TW202214791A - Formulation of an organic functional material - Google Patents

Abstract

The present invention relates to a formulation containing at least one organic functional material and a mixture of three different organic solvents, a first organic solvent A, a second organic solvent B and a third organic solvent C, characterized in that the first organic solvent A has a boiling point in the range from 250 to 350 DEG C and a viscosity of ≥ 10 mPas, the second organic solvent B has a boiling point in the range from 200 to 350 DEG C and a viscosity in the range from 2 to 5 mPas and the third organic solvent C has a boiling point in the range from 100 to 300 DEG C and a viscosity of ≤ 3 mPas, the solubility of the at least one organic functional material in the second organic solvent B is ≥ 5 g/l, and the boiling point of the first organic solvent A is at least 10 DEG C higher than the boiling point of the second organic solvent B, to the use of this formulation for the preparation of electronic devices as well as to electronic devices prepared by using these formulations.

Description

Formulation of organic functional materials

The present invention relates to a formulation containing at least one organic functional material and a mixture of three different organic solvents (a first organic solvent A, a second organic solvent B and a third organic solvent C), characterized in that: - The boiling point of the first organic solvent A is in the range of 250 to 350°C and the viscosity is ≥10 mPas, - the boiling point of the second organic solvent B is in the range of 200 to 350°C and the viscosity is in the range of 2 to 5 mPas, and - the boiling point of the third organic solvent C is in the range of 100 to 300°C and the viscosity is ≤3 mPas, - the solubility of at least one organic functional material in the second organic solvent B is ≥5 g/l, and - the boiling point of the first organic solvent A is at least 10°C higher than the boiling point of the second organic solvent B; And with respect to electroluminescent devices prepared using these formulations.

Organic Light Emitting Devices (OLEDs) have long been fabricated by vacuum deposition processes. Other technologies such as ink jet printing have recently been thoroughly investigated due to their advantages such as cost savings and the possibility of scaling up. One of the main challenges of multi-layer printing is to determine the relevant parameters for uniform deposition of ink on the substrate. To trigger these parameters, such as surface tension, viscosity or boiling point, some additives can be added to the formulation.

Technical problem and purpose of the present invention

Numerous solvents have been proposed for use in organic electronic devices for ink jet printing. However, the number of important parameters at play in the deposition and drying process makes solvent selection extremely challenging. Accordingly, there remains a need for improved organic semiconductor-containing formulations for deposition by ink jet printing. It is an object of the present invention to provide an organic semiconductor formulation that allows controlled deposition to form organic semiconductor layers with good layer properties and efficient performance. Another object of the present invention is to provide an organic semiconductor formulation which, when deposited on a substrate using, for example, ink jet printing and dried, achieves excellent film uniformity, resulting in good layer properties and efficient performance.

JP 2015/191792 A2 discloses a solute, which is composed of a constituent material of a functional layer or a precursor thereof, and is dissolved in a first solvent and a second solvent, wherein the first solvent has a first solubility parameter and a first Boiling point and the second solvent has a second solubility parameter smaller than the first solubility parameter and a second boiling point lower than the first boiling point, the first boiling point is ≥ 250 ℃ and the second boiling point is ≥ 170 ℃, and the second boiling point is the same as the first boiling point. The difference between the boiling points is > 40°C, and the second solubility parameter is 9.0 (cal/cm ³ ) ^1/2 or less.

EP 2924083 A1 discloses an ink for forming a functional layer, the ink comprises: a first component as a solute; a second component, whose boiling point is in the range of 280 to 350° C., is a good solvent for the first component , and is at least one selected from the group consisting of aromatic hydrocarbons including at least two aromatic rings, aromatic glycol ethers, aliphatic glycol ethers, aliphatic acetates and aliphatic esters; and The three-component, whose boiling point is in the range of 200 to 300 °C, is a good solvent for the first component, and is at least one selected from aromatic hydrocarbons, aromatic ethers and aliphatic ethers, wherein the second component is included in the third component. The ratio in the mixed solvent of the second component and the third component is 10% by weight or more.

A functional layer ink for forming a functional layer by a liquid coating method is disclosed in US 2013/256636 A1, wherein the functional layer material contains a macromolecular or low molecular weight material and a mixed solvent containing 0.1 wt % or more For solvent A with a viscosity of 0.01 to 0.05 Pa.s and solvent B with a viscosity of less than 0.01 Pa.s and a boiling point lower than that of solvent A, the mixed solvent has a viscosity of less than 0.02 Pa.s and a boiling point in the range of 200 to 350°C.

WO 2005/083814 A1 discloses a solution of at least one organic semiconductor containing at least one high molecular weight component in a solvent mixture of at least three different solvents A, B and C. Solvents A and B are good solvents for organic semiconductors, while solvent C is a poor solvent for organic semiconductors.

WO 2005/112145 A1 discloses a single-phase liquid composition (solution) comprising: at least one organic semiconductor comprising at least one high molecular weight component, and at least one organic solvent A which is a good solvent for organic semiconductors and at least one organic semiconductor Organic solvent B, which is a poor solvent for semiconductors, is a single-phase liquid composition characterized by the following conditions for the boiling points (b.p.) of solvents A and B: b.p.(A) > b.p.(B). [Problem solution]

The above object of the present invention is solved by providing a formulation containing at least one organic functional material and a mixture of three different organic solvents (first organic solvent A, second organic solvent B and third organic solvent C), which It is characterized in that the boiling point of the first organic solvent A is in the range of 250 to 350°C and the viscosity is ≥ 10 mPas, the boiling point of the second organic solvent B is in the range of 200 to 350°C and the viscosity is in the range of 2 to 5 In the range of mPas, the boiling point of the third organic solvent C is in the range of 100 to 300 °C and the viscosity is ≤3 mPas, the solubility of the at least one organic functional material in the second organic solvent B is ≥5 g/ l, and the boiling point of the first organic solvent A is at least 10°C higher than the boiling point of the second organic solvent B. [Benefits of the present invention]

The inventors have surprisingly found that the use of the formulations of the present invention allows efficient ink deposition to form uniform and well-defined organic layers of functional materials with good layer properties and performance.

The present invention relates to a formulation containing at least one organic functional material and a mixture of three different organic solvents (a first organic solvent A, a second organic solvent B and a third organic solvent C), characterized in that the first organic solvent A The boiling point of the second organic solvent B is in the range of 250 to 350°C and the viscosity is ≥10 mPas, the boiling point of the second organic solvent B is in the range of 200 to 350°C and the viscosity is in the range of 3 to 5 mPas, and the The boiling point of the three organic solvents C is in the range of 100 to 300°C and the viscosity is ≤3 mPas, the solubility of the at least one organic functional material in the second organic solvent B is ≥5 g/l, and the first organic solvent The boiling point of solvent A is at least 10°C higher than the boiling point of the second organic solvent B. Preferred specific example

In a first preferred embodiment of the present invention, the formulation contains at least one organic functional material and a solvent mixture, wherein the solvent mixture is composed of three different organic solvents (a first organic solvent A, a second organic solvent B and a third organic solvent Organic solvent C) composition, characterized in that the boiling point of the first organic solvent A is in the range of 250 to 350°C and the viscosity is ≥ 10 mPas, and the boiling point of the second organic solvent B is in the range of 200 to 350°C and the viscosity is in the range of 200 to 350°C It is in the range of 2 to 5 mPas, and the boiling point of the third organic solvent C is in the range of 100 to 300 °C and the viscosity is ≤3 mPas, and the solubility of the at least one organic functional material in the second organic solvent B is ≥5 g/l, and the boiling point of the first organic solvent A is at least 10°C higher than the boiling point of the second organic solvent B.

Based on the total amount of organic solvents in the formulation, the content of the first organic solvent A is 0.1 to 50% by volume, more preferably 0.1 to 25% by volume, more preferably 0.1 to 10% by volume, and optimally 0.1 to 5% by volume.

In another preferred embodiment, the formulation is characterized in that the first organic solvent A is selected from naphthalene derivatives, partially hydrogenated naphthalene derivatives (such as tetrahydronaphthalene derivatives), fully hydrogenated naphthalene derivatives (such as decahydronaphthalene derivatives), indane derivatives and fully hydrogenated anthracene derivatives.

The expression "derivative" as used in the context of this case means a core structure, such as a naphthalene nucleus or a partially/fully hydrogenated naphthalene nucleus, at least mono- or polysubstituted by the substituent R. R is the same or different in each of the following cases: - a straight-chain alkyl group having 1 to 12 carbon atoms or a branched or cyclic alkyl group having 3 to 12 carbon atoms in which one or more non-adjacent CH The ₂ group may be substituted by -O-, -S-, -NR ¹ -, -CO-O-, -C=O-, -CH=CH- or -C≡C-, and one or more hydrogen Atoms may be substituted with F or aryl or heteroaryl groups having 4 to 14 carbon atoms and may be substituted with ^one or more non-aromatic R groups, and on the same ring or on as many as two different rings The substituents R1 may be taken together in turn to form ^a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by multiple substituents R1, or two ^Rs may be taken together to form a ring system having 4 to 14 carbons A monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system of atoms which may be substituted by multiple substituents R ¹ , or - has 4 to 14 carbon atoms and may be substituted by one or more non-aromatic R Aryl or heteroaryl substituted by ¹ group, and multiple substituents R ¹ on the same ring or on two different rings can be taken together in turn to form a monocyclic or polycyclic ring that can be substituted by multiple substituents R ¹ , aliphatic, aromatic, or heteroaromatic ring systems, or two ^Rs may be taken together to form a monocyclic or polycyclic, aliphatic, aromatic, or Heteroaromatic ring systems.

In a more preferred embodiment, the formulation is characterized in that the first organic solvent A is selected from the group consisting of naphthalene derivatives, tetrahydronaphthalene derivatives and decahydronaphthalene derivatives.

其中 R    係 - 具有1至12個碳原子之直鏈烷基或具有3至12個碳原子之分支或環狀烷基，其中一或多個不相鄰之CH ₂基團可被-O-、-S-、-NR ¹-、-CO-O-、-C=O-、-CH=CH-或-C≡C-取代，且其中一或多個氫原子可被F或具有4至14個碳原子並可被一或多個非芳族R ¹基團取代之芳基或雜芳基取代，且在同一環上或在兩個不同環上之多個取代基R ¹可一起依次形成可被多個取代基R ¹取代的單環或多環、脂族、芳族或雜芳族環系統，或 - 具有4至14個碳原子並可被一或多個非芳族R ¹基團取代的芳基或雜芳基，且在同一環上或在兩個不同環上之多個取代基R ¹可一起依次形成可被多個取代基R ¹取代的單環或多環、脂族、芳族或雜芳族環系統，或兩個R可一起形成具有4至14個碳原子之可被多個取代基R ¹取代的單環或多環、脂族、芳族或雜芳族環系統，且 R ¹在各情況下為相同或不同，並係具有1至12個碳原子之直鏈烷基或烷氧基或具有3至20個碳原子之分支或環狀烷基或烷氧基，其中一或多個不相鄰之CH ₂基團可被 -O-、-S-、-CO-O-、-C=O-、-CH=CH-或-C≡C-取代。 If the first organic solvent A is a naphthalene derivative, it is preferably a solvent according to the general formula (I)

wherein R is - a straight-chain alkyl group having 1 to 12 carbon atoms or a branched or cyclic alkyl group having 3 to 12 carbon atoms, wherein one or more non-adjacent _CH groups may be replaced by -O- , -S-, -NR ¹ -, -CO-O-, -C=O-, -CH=CH- or -C≡C- substituted, and one or more of the hydrogen atoms may be F or have 4 to 14 carbon atoms may be substituted by one or more non-aromatic R ¹ groups substituted with aryl or heteroaryl groups, and multiple substituents R ¹ on the same ring or on two different rings may be taken together in sequence form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which may be substituted by multiple substituents R ¹ , or - has 4 to 14 carbon atoms and may be substituted by one or more non-aromatic R ¹ aryl or heteroaryl substituted by a group, and multiple substituents R ¹ on the same ring or on two different rings can be taken together in turn to form a monocyclic or polycyclic ring, which can be substituted by multiple substituents R ¹ , aliphatic, aromatic or heteroaromatic ring systems, or two Rs may be taken together to form a monocyclic or polycyclic, aliphatic, aromatic or heterocyclic having 4 to ¹⁴ carbon atoms which may be substituted by multiple substituents R1 Aromatic ring systems, where R ¹ is in each case the same or different, and is a straight-chain alkyl or alkoxy group having 1 to 12 carbon atoms or a branched or cyclic alkyl group having 3 to 20 carbon atoms or alkoxy, where one or more non-adjacent _CH2 groups may be replaced by -O-, -S-, -CO-O-, -C=O-, -CH=CH- or -C≡C -replace.

Preferably, R is a cyclic alkyl group with 6 to 10 carbon atoms, wherein one or more non-adjacent CH ₂ groups can be replaced by -O-, -S-, -NR ¹ -, -CO- O-, -C=O-, -CH=CH- or -C≡C- substituted; or an aryl or heteroaryl group having 6 to 10 carbon atoms which may be substituted by one or more substituents R ¹ , And a plurality of substituents R ¹ on the same ring or on two different rings can be taken together in turn to form a monocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ring system which can be substituted by a plurality of substituents R ¹ .

In the first preferred embodiment, the naphthalene derivative is 1-cyclohexylnaphthalene or 1-phenylnaphthalene.

其中R可具有如上關於式(I)所給予之含義。 If the first organic solvent A is a tetrahydronaphthalene derivative, it is preferably a solvent according to the general formula (II) or (III)

wherein R may have the meanings given above for formula (I).

In a second preferred embodiment, the tetrahydronaphthalene derivative is 1-phenyl-1,2,3,4-tetrahydronaphthalene.

其中R可具有如上關於式(I)所給予之含義。 If the first organic solvent A is a tetrahydronaphthalene derivative, it is preferably a solvent according to the general formula (IV)

wherein R may have the meanings given above for formula (I).

In a third preferred embodiment, the tetrahydronaphthalene derivative is 1-cyclohexyldecalin or 1-phenyldecalin.

The boiling point of the first organic solvent A is in the range of 250 to 350°C, preferably in the range of 260 to 340°C, and most preferably in the range of 270 to 330°C.

The melting point of the first organic solvent A is preferably lower than 25°C, which means that the first organic solvent A is liquid at room temperature.

The viscosity of the first organic solvent A is ≥10 mPas, preferably ≥15 mPas, more preferably ≥25 mPas, and most preferably ≥50 mPas.

The solubility of at least one organic functional material in the first organic solvent A is ≥5 g/l.

Table 1 below shows examples of preferred first organic solvents A and their boiling points (BP) and melting points (MP).

The formulation of the present case comprises a second organic solvent B different from the first organic solvent A and the third organic solvent C. The second organic solvent B is used together with the first organic solvent A and the third organic solvent C.

The content of the second organic solvent B is based on the total amount of organic solvents in the formulation, preferably in the range of 20 to 85% by volume, more preferably in the range of 30 to 80% by volume, and most preferably in the range of 40 to 75% by volume.

A suitable second organic solvent B is preferably an organic solvent, which especially includes ketones, ethers, esters, amides such as di-C _1-2 alkylcarboxamides, sulfur compounds, nitro compounds, hydrocarbons, halogenated hydrocarbons (such as chlorinated hydrocarbons), aromatic or heteroaromatic hydrocarbons (eg naphthalene derivatives) and halogenated aromatic or heteroaromatic hydrocarbons.

Preferably, the second organic solvent B can be selected from one of the following groups: substituted and unsubstituted aromatic or linear ethers such as 3-phenoxytoluene or anisole; substituted or unsubstituted Aromatic derivatives such as cyclohexylbenzene; substituted or unsubstituted indanes such as hexamethylindenane; substituted and unsubstituted aromatic or linear ketones such as dicyclohexyl ketone; substituted and unsubstituted Heterocycles such as pyrrolidone, pyridine, pyrazine; other fluorinated or chlorinated aromatic hydrocarbons, substituted or unsubstituted naphthalenes such as alkyl-substituted naphthalenes such as 1-ethylnaphthalene.

Particularly preferred second organic solvent B is 1-ethylnaphthalene, 2-ethylnaphthalene, 2-propylnaphthalene, 2-(1-methylethyl)-naphthalene, 1-(1-methylethyl) -Naphthalene, 2-butylnaphthalene, 1,6-dimethylnaphthalene, 2,2'-dimethylbiphenyl, 3,3´-dimethylbiphenyl, 1-acetylnaphthalene, 1,2, 3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1,2,4-trichlorobenzene, 1,2-dichlorobenzene Hydronaphthalene, 1,2-dimethylnaphthalene, 1,3-benzobisoxazole, 1,3-diisopropylbenzene, 1,3-dimethylnaphthalene, 1,4-benzodioxane , 1,4-diisopropylbenzene, 1,4-dimethylnaphthalene, 1,5-dimethyltetrahydronaphthalene, 1-benzothiophene, thiaphthalene, 1-bromonaphthalene, 1-chloro- Methylnaphthalene, 1-methoxynaphthalene, 1-methylnaphthalene, 2-bromo-3-bromomethylnaphthalene, 2-bromomethylnaphthalene, 2-bromonaphthalene, 2-ethoxynaphthalene, 2-iso Propylanisole, 3,5-dimethylanisole, 5-methoxyindan, 5-methoxyindole, 5-tert-butyl-m-xylene, 6-methylquinoline Linen, 8-methylquinoline, acetophenone, benzothiazole, benzyl acetate, butylphenyl ether, cyclohexylbenzene, decalin, dimethoxytoluene, 3-phenoxytoluene, Diphenyl ether, propiophenone, hexylbenzene, hexamethylindan, isochromane, phenyl acetate, propiophenone, veratrol, pyrrolidone, N,N-dibutylaniline, cyclohexyl hexanoate, Menthyl isovalerate, dicyclohexyl ketone, ethyl laurate, ethyl caprate.

The boiling point of the second organic solvent B is in the range of 200 to 350°C, preferably in the range of 225 to 325°C, and most preferably in the range of 250 to 300°C.

The viscosity of the second organic solvent B is in the range of 2 to 5 mPas, preferably in the range of 2.5 to 5 mPas, more preferably in the range of 3 to 5 mPas, most preferably >3 to 5 mPas In the range.

The solubility of at least one organic functional material in the second organic solvent B is ≥5 g/l, preferably ≥10 g/l.

Table 2 below shows examples of preferred second organic solvents B and their boiling points (BP) and melting points (MP).

The formulation of the present case contains a third organic solvent C different from the first organic solvent A and the second organic solvent B. The third organic solvent C is used together with the first organic solvent A and the second organic solvent B.

The content of the third organic solvent C is based on the total amount of organic solvents in the formulation, preferably in the range of 10 to 70% by volume, more preferably in the range of 15 to 60% by volume, and most preferably in the range of 20 to 50% by volume volume%.

Suitable third organic solvents C are preferably organic solvents, which include especially ketones, substituted and unsubstituted aromatic, cycloaliphatic or linear ethers, esters, amides, aromatic amines, sulfur compounds, nitro groups Compounds, hydrocarbons, halogenated hydrocarbons (eg chlorinated hydrocarbons), aromatic or heteroaromatic hydrocarbons (eg naphthalene derivatives, pyrrolidones, pyridines, pyrazines), indane derivatives and halogenated aromatic or heteroaromatic hydrocarbons.

Preferably, the third organic solvent C may be selected from one of the following groups: aliphatic hydrocarbons, alkylbenzenes, cycloalkylbenzenes, aromatic ethers, aromatic and non-aromatic esters, cyclic esters.

The boiling point of the third organic solvent C is in the range of 100 to 300°C, preferably in the range of 125 to 275°C, and most preferably in the range of 150 to 250°C. Furthermore, the boiling point of the third organic solvent C is lower than the boiling point of the second solvent B by at least 10°C, preferably at least 20°C, more preferably at least 30°C.

The viscosity of the third organic solvent C is ≤3 mPa·s, preferably ≤2.5 mPa·s, more preferably ≤2 mPa·s.

The solubility of at least one organic functional material in the second organic solvent B is ≥5 g/l, preferably ≥10 g/l.

Table 3 below shows examples of particularly preferred third organic solvent C and its boiling point (BP) and melting point (MP).

In a second preferred embodiment of the present invention, the formulation is free of solvents containing groups capable of accepting or donating hydrogen bonds. This means that in preferred embodiments, the formulations of the present invention are free of solvents containing groups capable of accepting or donating hydrogen bonds.

The content of at least one organic functional material in the formulation is in the range of 0.001 to 20% by weight, preferably in the range of 0.01 to 10% by weight, more preferably in the range of 0.001 to 20% by weight, based on the total weight of the formulation. In the range of 0.1 to 5% by weight, most preferably in the range of 0.3 to 5% by weight.

Furthermore, the viscosity of the formulation of the present invention is preferably in the range of 0.8 to 50 mPas, more preferably in the range of 1 to 40 mPas, most preferably in the range of 2 to 15 mPas.

The viscosities of formulations and solvents according to the present invention were measured using a 1° cone-plate rotational rheometer, Discovery Model AR3 (Thermo Scientific). The equipment can precisely control temperature and shear rate. Viscosity measurements were made at a temperature of 25.0°C (+/- 0.2°C) and a shear rate of 500 s ⁻¹ . Each sample was measured three times, and the obtained measurements were averaged.

The surface tension of the formulations of the present invention is preferably in the range of 10 to 70 mN/m, more preferably in the range of 15 to 50 mN/m, most preferably in the range of 20 to 40 mN/m.

Preferably, the surface tension of the organic solvent mixture is in the range of 10 to 70 mN/m, more preferably in the range of 15 to 50 mN/m, most preferably in the range of 20 to 40 mN/m.

Surface tension can be measured at 20°C using an FTA (First Ten Angstrom) 1000 contact angle goniometer. Details of this method can be obtained from First Ten Angstrom in accordance with "Surface Tension Measurements Using the Drop Shape Method" by Dr. Roger P. Woodward. Preferably, the pendant drop method can be used to measure the surface tension. This measurement technique distributes droplets on the needle into a bulk liquid or gas phase. The shape of the droplet depends on the relationship between surface tension, gravity and density difference. Using the hanging drop method, the surface tension was calculated from the shadow image of the hanging drop using http://www.kruss.de/services/education-theory/glossary/drop-shape-analysis. All surface tension measurements were performed using a commonly used and commercially available high precision drop shape analysis instrument, in other words the FTA1000 from First Ten Ångstrom. Surface tension was measured by software FTA1000. All measurements were performed at room temperature in the range between 20°C and 25°C. Standard operating procedure involves measuring the surface tension of each formulation using a fresh disposable drop dispensing system (syringe and needle). Each drop was measured for a duration of one minute, 60 measurements were taken and then averaged. Three drops were measured for each formulation. The final value is the average of the preceding measurements. Various liquids with well-known surface tensions are regularly cross-checked with this instrument.

Formulations according to the present invention comprise at least one organic functional material that can be used to fabricate functional layers of electronic devices. Functional materials are generally organic materials added between the anode and cathode of an electronic device.

The expression organic functional material especially denotes organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light-absorbing compounds, organic light-sensitive compounds, organic photosensitizers and other organic photosensitive compounds. The term organic functional material additionally includes organometallic complexes of transition metals, rare earths, lanthanides and actinides.

The organic functional material is preferably an organic semiconductor selected from the group consisting of fluorescent emitters, phosphorescent emitters, host materials, host materials, exciton-blocking materials, electron transport materials, electron Implantation materials, hole transport materials, hole injection materials, n-type dopants, p-type dopants, wide bandgap materials, electron blocking materials, and hole blocking materials.

Preferred specific examples of organic functional materials are disclosed in detail in WO 2011/076314 A1, which is incorporated into the present application by reference.

In a more preferred embodiment, the organic semiconductor is a luminescent material selected from the group consisting of fluorescent emitters and phosphorescent emitters.

The organic functional material can be a low molecular weight compound, polymer, oligomer or dendrimer, wherein the organic functional material can also be in the form of a mixture. Thus, formulations according to the present invention may comprise two or more compounds of low molecular weight, one compound of low molecular weight and one polymer or two polymers (mixtures).

If the organic functional material is a low molecular weight compound, its molecular weight is preferably ≤3,000 g/mol, more preferably ≤2,000 g/mol, and most preferably ≤1,000 g/mol.

If the organic functional material is a polymer, its molecular weight M _w is preferably ≥10,000 g/mol, more preferably ≥20,000 g/mol, and most preferably ≥40,000 g/mol.

Here, the molecular weight M _w of the polymer is preferably in the range of 10,000 to 2,000,000 g/mol, more preferably in the range of 20,000 to 1,000,000 g/mol, most preferably in the range of 40,000 to 300,000 g/mol Inside. The molecular weight _Mw is determined by GPC (=gel permeation chromatography) relative to the internal standard polystyrene.

In a third preferred embodiment of the present invention, at least one organic functional material in the formulation of the present invention is a low molecular weight compound. Preferably, all organic functional materials in the formulation of the present case are low molecular weight compounds.

In another preferred embodiment, the at least one emissive material is a mixture of two or more different compounds having low molecular weights.

Organic functional materials are often described by the property of frontier orbital, which will be described in more detail below. Molecular orbitals, especially the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), their energy levels and the energy of the lowest triplet state T ₁ or lowest excited singlet state S ₁ of the material can be estimated according to quantum chemistry . To calculate these properties of metal-free organic substances, geometric optimization was first performed using the "ground state/semi-empirical/Default Spin/AM1/charge 0/spin singlet" method. The energy calculation is then performed according to the optimized geometry. Here the "TD-SCF/DFT/Preset Spin/B3PW91" method was used, using the "6-31G(d)" base set (charge 0, spin singlet). For metal-containing compounds, the geometry was optimized via the "Ground State/Hartree-Fock/Default Spin/LanL2MB/Charge 0/Spin Singlet" method. The energy calculations were performed similarly to the method described above for organic substances, except that the "LanL2DZ" basis function group was used for the metal atoms, and the "6-31G(d)" basis function group was used for the ligands. The energy calculation gives the HOMO energy level HEh or the LUMO energy level LEh expressed in hartree units. The HOMO and LUMO energy levels calibrated in electron volts according to cyclic voltammetry measurement are determined by the following formula: HOMO(eV) = ((HEh*27.212)-0.9899)/1.1206 LUMO(eV) = ( (LEh*27.212)-2.0041)/1.385

For the purposes of this case, these values are considered to be the HOMO and LUMO levels of the material, respectively.

The lowest triplet state T ₁ is defined as the triplet state energy with the lowest energy resulting from the quantum chemical calculations described.

The lowest excited singlet state S ₁ is defined as the excited singlet state energy with the lowest energy resulting from the quantum chemical calculations described.

The method described here is independent of the software package used and always gives the same results. Examples of programs frequently used for this purpose are "Gaussian09W" (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).

Compounds with hole-injecting properties, also referred to herein as hole-injecting materials, simplify or facilitate the transfer of holes (ie, positive charges) from the anode into the organic layer. Generally, the hole injecting material has a HOMO level near the anode level or higher, ie, typically at least -5.3 eV.

Compounds with hole transport properties, also referred to herein as hole transport materials, are capable of transporting holes, ie positive charges, which are typically injected from the anode or an adjacent layer such as a hole injection layer. Hole transport materials generally have a high HOMO level, preferably at least -5.4 eV. Depending on the structure of the electronic device, hole transport materials may also be used as hole injection materials.

Preferred compounds with hole injection and/or hole transport properties include, for example, triarylamine, benzidine, tetraaryl-p-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrogen Phenazine, thianthene, dibenzo-p-dioxin, phenoxathiynes, carbazole, azulene, thiophene, pyrrole and furan and their derivatives and others with high HOMO (HOMO=highest occupied molecular orbital) Heterocycle containing O, S or N.

Compounds with electron injection and/or electron transport properties are e.g. pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoline, anthracene, benzanthracene, pyrene, perylene, benzimidazole, triazine , ketones, phosphine oxides and phenazines and their derivatives, as well as triarylboranes and other O, S or N containing heterocycles with low LUMO (LUMO = lowest occupied molecular orbital).

The formulations of the present invention preferably comprise an emitter. The term emitter means a material that upon excitation can occur by any type of energy transfer, allowing a radiative transition to a ground state and emitting light. In general, two types of emitters are known, in other words fluorescent emitters and phosphorescent emitters. The term fluorescent emitter means a material or compound that undergoes a radiative transition from an excited singlet state to a ground state. The expression phosphorescent emitter preferably denotes a transition metal-containing luminescent material or compound.

If the dopant induces the above-mentioned properties in the system, the emitter is often also referred to as a dopant. A dopant in a system comprising a host material and a dopant means a component in a smaller proportion in the mixture. Correspondingly, host material in a system comprising host material and dopant means a component in a larger proportion in the mixture. Thus, the expression phosphorescent emitter may also mean, for example, a phosphorescent dopant.

Compounds that emit light include, inter alia, fluorescent and phosphorescent emitters. These include in particular those containing stilbene, stilbene, styrylamine, coumarin, rubrene, rhodamine, thiazole, thiadiazole, cyanine, thiophene, paraphenylene, perylene , phthalocyanine, porphyrin, ketone, quinoline, imine, anthracene and/or pyrene structure compound. Particularly preferred are compounds that emit light with high efficiency from the triplet state even at room temperature, ie exhibit electrophosphorescence rather than electrofluorescence, which often leads to increased energy efficiency. Suitable for this purpose are primarily compounds containing heavy atoms with atomic numbers greater than 36. A compound containing a d or f transition metal satisfying the above conditions is preferred. Particularly preferred here are corresponding compounds containing Group 8 to 10 elements (Ru, Os, Rh, Ir, Pd, Pt). Suitable functional compounds here are, for example, various complexes, as described, for example, in WO 02/068435 A1, WO 02/081488 A1, EP 1239526 A2 and WO 2004/026886 A2.

Preferred compounds useful as fluorescent emitters are described by the following examples. Preferred fluorescent emission systems are selected from the group consisting of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, styryl phosphines, styryl ethers and aromatic amines.

Monostyrylamine means a compound containing one substituted or unsubstituted styryl group and at least one amine, preferably an aromatic amine. Distyrylamine means a compound containing two substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. Tristyrylamine means a compound containing three substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. Tetrastyrylamine means a compound containing four substituted or unsubstituted styryl groups and at least one amine, preferably an aromatic amine. The styryl group is particularly preferably stilbene, which can also be further substituted. The corresponding phosphines and ethers are defined similarly to amines. In the sense of the present invention, arylamine or aromatic amine means a compound containing three substituted or unsubstituted aromatic or heteroaromatic ring systems bonded directly to nitrogen. At least one of these aromatic or heteroaromatic ring systems is preferably a fused ring system, preferably having at least 14 aromatic ring atoms. Preferred examples thereof are aromatic anthraceneamines, aromatic anthracenediamines, aromatic pyreneamines, aromatic pyrenediamines, aromatic chrysenamines or aromatic chrysenamines. Aromatic anthracenamine means a compound in which a diarylamine group is directly bonded to an anthracene group, preferably at the 9-position. Aromatic anthracenediamine means a compound in which two diarylamine groups are directly bonded to an anthracene group, preferably at the 2,6- or 9,10-position. Aromatic pyreneamine, pyrenediamine, pyreneamine and pyrenediamine are similarly defined, wherein the diarylamine group is preferably bonded to the 1-position or 1,6-position of pyrene.

More preferred fluorescent emission systems are selected from indenoindenamines or indenediamines, which are described in particular in WO 2006/122630; WO 2008/006449; and dibenzoindenoindenamines or dibenzoindenosediamines, which are described in particular in WO 2007/140847.

Examples of styrylamines useful as fluorescent emitters are substituted or unsubstituted tristyrylamines or WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549 and Dopants as described in WO 2007/115610. Distyrylbenzene and distyrylbiphenyl derivatives are described in US 5121029. Other styrylamines can be found in US 2007/0122656 A1.

Particularly preferred styrylamine compounds are the compounds of formula EM-1 described in US 7250532 B2 and the compounds of formula EM-2 described in DE 10 2005 058557 A1:

Particularly preferred triarylamine compounds are the formula EM-3 disclosed in CN 1583691 A, JP 08/053397 A and US 6251531 B1, EP 1957606 A1, US 2008/0113101 A1, US 2006/210830 A, WO 2008/006449 and DE 102008035413 Compounds to EM-15 and their derivatives:

Other preferred compounds that can be used as fluorescent emitters are selected from derivatives of the following compounds: naphthalene, anthracene, condensed tetraphenyl, benzanthracene, triphenylene (DE 10 2009 005746), fluorine, fluoranthene, diindene Periflanthene, indenoperylene, phenanthrene, perylene (US 2007/0252517 A1), pyrene, chrysene, decacycloene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentane Diene, pyran, helicene, rubrene, coumarin (US 4769292, US 6020078, US 2007/0252517 A1), pyran, oxazole, benzoxazole, benzothiazole, benzimidazole, pyrazine , cinnamate, diketopyrrolopyrrole, acridone and quinacridone (US 2007/0252517 A1).

Among the anthracene compounds, particularly preferred are 9,10-substituted anthracenes such as 9,10-dibenzoanthracene and 9,10-bis(phenylethynyl)anthracene. 1,4-Bis(9'-ethynthryl)benzene is also a preferred dopant.

Also preferred are derivatives of rubrene, coumarin, rhodamine, quinacridone such as DMQA (=N,N'-dimethylquinacridone), dicyanomethylpyran such as DCM ( =4-(dicyanoethylidene)-6-(4-dimethylaminostyryl-2-methyl)-4H-pyran), thiopyran, polymethine, pyridinium ( pyrylium) and thiapyrylium salts, bisindenoperylene and indenoperylene.

The blue fluorescent emitters are preferably polyaromatic compounds such as 9,10-bis(2-naphthanthracene) and other anthracene derivatives, fused tetraphenyl, xanthene, perylene derivatives such as 2,5,8, 11-Tetra-tert-butylperylene, phenylene such as 4,4'-bis(9-ethyl-3-carbazolidene)-1,1'-biphenyl, perylene, fluoranthene, aryl pyrene (US 2006/0222886 A1), arylidene vinylidene (US 5121029, US 5130603), bis(azinyl)imine-boron compound (US 2007/0092753 A1), bis(azinyl)methane Compounds and carbon styryl compounds.

More preferred blue fluorescent emitting systems are described in C.H. Chen et al.: "Recent developments in organic electroluminescent materials" Macromol. Symp. 125, (1997) 1-48 and "Recent progress of molecular organic electroluminescent materials and devices" Mat. Sci and Eng. R, 39 (2002), 143-222.

其中以下適用於所使用之符號和指數： Ar ¹、Ar ²、Ar ³在各自情況下相同或不同地為具有5至30個芳族環原子之芳基或雜芳基，其可被一或多個基團R ¹取代，附帶條件為Ar ²不代表蒽、稠四苯或稠五苯； X 在各自情況下相同或不同地為選自BR ²、C(R ²) ₂、Si(R ²) ₂、C=O、C=NR ²、C=C(R ²) ₂、O、S、S=O、SO ₂、NR ²、PR ²、P(=O)R ²及P(=S)R ²之群組； R ¹、R ²在各自情況下相同或不同地為H、D、F、Cl、Br、I、N(Ar ⁴) ₂、C(=O)Ar ⁴、P(=O)(Ar ⁴) ₂、S(=O)Ar ⁴、S(=O) ₂Ar ⁴、CR ²=CR ²Ar ⁴、CHO、CR ³=C(R ³) ₂、CN、NO ₂、Si(R ³) ₃、B(OR ³) ₂、B(R ³) ₂、B(N(R ³) ₂) ₂、OSO ₂R ³、各自可被一或多個基團R ³取代的具有1至40個碳原子之直鏈烷基、烷氧基或硫代烷氧基或具有2至40個碳原子之直鏈烯基或炔基或具有3至40個碳原子之分支或環狀烷基、烯基、炔基、烷氧基或硫代烷氧基，其中在各自情況下一或多個不相鄰之CH ₂基團可被R ³C=CR ³、C≡C、Si(R ³) ₂、Ge(R ³) ₂、Sn(R ³) ₂、C=O、C=S、C=Se、C=NR ³、P(=O)R ³、SO、SO ₂、NR ³、O、S或CONR ³取代，且其中一或多個氫原子可被F、Cl、Br、I、CN或NO ₂，或在各自情況下可被一或多個基團R ³取代的具有5至60個芳族環原子之芳族或雜芳族環系統，或這些系統之組合取代；在此二或更多個取代基R ¹或R ²也可彼此形成單環或多環之脂族或芳族環系統； R ³在各自情況下相同或不同地為H、D或具有1至20個碳原子之脂族或芳族烴基； Ar ⁴在各自情況下相同或不同地為可被一或多個非芳族基團R ¹取代之具有5至30個芳族環原子之芳族或雜芳族環系統；於同一氮或磷原子上的兩個基團Ar也可藉由單鍵或橋X彼此連接； m、n 為0或1，附帶條件為m+n=1； p 為1、2、3、4、5或6； 在此Ar ¹、Ar ²和X一起形成五元環或六元環，及Ar ²、Ar ³和X一起形成五元環或六元環，附帶條件為式(1)之化合物中所有符號X皆結合於五元環中或式(1)之化合物中所有符號X皆結合於六元環中； 其特徵為若p=1時基團Ar ¹、Ar ²和Ar ³中所有π電子之總和為至少28個，若p=2時為至少34個，且若p=3時為至少40個，且若p=4時為至少46個，且若p=5時為至少52，且若p=6時為至少58； 在此n=0或m=0意指對應之基團X不存在，取而代之地將氫或取代基R ¹鍵合至Ar ²和Ar ³之對應位置。 Hydrocarbons of the following formula (1) disclosed in WO 2010/012328 A1 as a better blue fluorescent emission system.

where the following apply to the symbols and indices used: Ar ¹ , Ar ² , Ar ³ are in each case identically or differently an aryl or heteroaryl radical having 5 to 30 aromatic ring atoms, which can be represented by one or Multiple radicals R ¹ are substituted, with the proviso that Ar ² does not represent anthracene, fused tetraphenyl or fused pentaphenyl; X is in each case identically or differently selected from BR ² , C(R ² ) ₂ , Si(R ² ) ₂ , C=O, C=NR ² , C=C(R ² ) ₂ , O, S, S=O, SO ₂ , NR ² , PR ² , P(=O)R ² and P(= S) the group of R ² ; R ¹ , R ² are identically or differently in each case H, D, F, Cl, Br, I, N(Ar ⁴ ) ₂ , C(=O)Ar ⁴ , P (=O)(Ar ⁴ ) ₂ , S(=O)Ar ⁴ , S(=O) ₂ Ar ⁴ , CR ² =CR ² Ar ⁴ , CHO, CR ³ =C(R ³ ) ₂ , CN, NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , B(R ³ ) ₂ , B(N(R ³ ) ₂ ) ₂ , OSO ₂ R ³ , each may be replaced by one or more groups R ³ Substituted straight-chain alkyl, alkoxy or thioalkoxy having 1 to 40 carbon atoms or straight-chain alkenyl or alkynyl having 2 to 40 carbon atoms or branched having 3 to 40 carbon atoms or cyclic alkyl, alkenyl, alkynyl, alkoxy or thioalkoxy, wherein in each case or more non-adjacent CH ₂ groups may be replaced by R ³ C=CR ³ , C≡ C, Si(R ³ ) ₂ , Ge(R ³ ) ₂ , Sn(R ³ ) ₂ , C=O, C=S, C=Se, C=NR ³ , P(=O)R ³ , SO, SO ₂ , NR ³ , O, S or CONR ³ , and one or more of these hydrogen atoms may be substituted by F, Cl, Br, I, CN or NO ₂ , or in each case by one or more groups R ³ substituted aromatic or heteroaromatic ring systems having 5 to 60 aromatic ring atoms, or a combination of these systems; here two or more substituents R ¹ or R ² may also form a monocyclic ring with each other or polycyclic aliphatic or aromatic ring systems; R ³ in each case identically or differently H, D or an aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms; Ar ⁴ in each case identical or variously aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms which may be substituted by ^one or more non-aromatic groups R; two groups Ar on the same nitrogen or phosphorus atom can also be connected to each other by single bonds or bridges X; m, n are 0 or 1, with the proviso that m+n=1; p is 1, 2, 3, 4, 5 or 6; here Ar ¹ , Ar ² together with X to form a five-membered or six-membered ring, and Ar ² , Ar ³ and X together form a five-membered ring or a six-membered ring, with the proviso that all symbols X in the compound of formula (1) are bound in a five-membered ring or in a compound of formula (1) all symbols X are bound in a six-membered ring; characterized if p= The sum of all pi electrons in the groups Ar ¹ , Ar ² and Ar ³ is at least 28 when 1, at least 34 if p=2, and at least 40 if p=3, and if p=4 is at least 46, and at least 52 if p=5, and at least 58 if p=6; where n=0 or m=0 means that the corresponding group X is not present, and instead a hydrogen or substituted The group R ¹ is bonded to the corresponding positions of Ar ² and Ar ³ .

其中： Ar ¹在各自情況下相同或不同地為可被一或多個基團R ¹取代的具有6至18個芳族環原子之芳基或雜芳基； Ar ²在各自情況下相同或不同地為可被一或多個基團R ²取代的具有6個芳族環原子之芳基或雜芳基； X ¹在各自情況下相同或不同地為BR ³、C(R ³) ₂、   -C(R ³) ₂-C(R ³) ₂-、-C(R ³) ₂-O-、-C(R ³) ₂-S-、-R ³C=CR ³-、  -R ³C=N-、Si(R ³) ₂、-Si(R ³) ₂-Si(R ³) ₂-、C=O、O、S、S=O、SO ₂、NR ³、PR ³或P(=O)R ³； R ¹、R ²、R ³在各自情況下相同或不同地為H、D、F、Cl、Br、I、C(=O)R ⁴、CN、Si(R ⁴) ₃、N(R ⁴) ₂、P(=O)(R ⁴) ₂、OR ⁴、S(=O)R ⁴、S(=O) ₂R ⁴、具有1至20個碳原子之直鏈烷基或烷氧基或具有3至20個碳原子之分支或環狀烷基或烷氧基或具有2至20個碳原子之烯基或炔基，其中上述基團可各自被一或多個基團R ⁴取代且其中上述基團中一或多個CH ₂基團可被-R ⁴C=CR ⁴-、-C≡C-、Si(R ⁴) ₂、C=O、C=NR ⁴、-C(=O)O-、-C(=O)NR ⁴-、NR ⁴、P(=O)(R ⁴)、-O-、-S-、SO或SO ₂取代，或在各自情況下可被一或多個基團R ⁴取代的具有5至30個芳族環原子之芳族或雜芳族環系統，其中二或更多個基團R ³可彼此連結並可形成環； R ⁴在各自情況下相同或不同地為H、D、F、Cl、Br、I、C(=O)R ⁵、CN、Si(R ⁵) ₃、N(R ⁵) ₂、P(=O)(R ⁵) ₂、OR ⁵、S(=O)R ⁵、S(=O) ₂R ⁵、具有1至20個碳原子之直鏈烷基或烷氧基或具有3至20個碳原子之分支或環狀烷基或烷氧基或具有2至20個碳原子之烯基或炔基，其中上述基團可各自被一或多個基團R ⁵取代且其中上述基團中一或多個CH ₂基團可被-R ⁵C=CR ⁵-、-C≡C-、Si(R ⁵) ₂、C=O、C=NR ⁵、  -C(=O)O-、-C(=O)NR ⁵-、NR ⁵、P(=O)(R ⁵)、-O-、-S-、SO或SO ₂取代，或在各自情況下可被一或多個基團R ⁵取代的具有5至30個芳族環原子之芳族或雜芳族環系統，其中二或更多個基團R ⁴可彼此連結並可形成環； R ⁵在各自情況下相同或不同地為H、D、F或具有1至20個碳原子之脂族、芳族或雜芳族有機基團，此外，其中一或多個氫原子可被D或F取代；在此二或更多個取代基R ⁵可彼此連結並可形成環； 其中兩個基團Ar ¹中之至少一個必定含有10個或更多個芳族環原子；及 其中，若兩個基團Ar ¹中之一個係苯基，則兩個基團Ar ¹中之另一個必定不含多於14個芳族環原子。 Other preferred blue fluorescent emission systems are hydrocarbons of the following formula (2) disclosed in WO 2014/111269 A2.

where: Ar ¹ in each case is identically or differently an aryl or heteroaryl group having 6 to 18 aromatic ring atoms which may be substituted by one or more radicals R ¹ ; Ar ² is identical in each case or variously aryl or heteroaryl groups having 6 aromatic ring atoms which may be substituted by one or more radicals R ² ; X ¹ is identically or differently in each case BR ³ , C(R ³ ) ₂ , -C(R ³ ) ₂ -C(R ³ ) ₂ -, -C(R ³ ) ₂ -O-, -C(R ³ ) ₂ -S-, -R ³ C=CR ³ -, -R ³ C=N-, Si(R ³ ) ₂ , -Si(R ³ ) ₂ -Si(R ³ ) ₂ -, C=O, O, S, S=O, SO ₂ , NR ³ , PR ³ or P(=O)R ³ ; R ¹ , R ² , R ³ are identically or differently in each case H, D, F, Cl, Br, I, C(=O)R ⁴ , CN, Si(R ⁴ ) ₃ , N(R ⁴ ) ₂ , P(=O)(R ⁴ ) ₂ , OR ⁴ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , with 1 to 20 carbon atoms Straight-chain alkyl or alkoxy or branched or cyclic alkyl or alkoxy having 3 to 20 carbon atoms or alkenyl or alkoxy having 2 to 20 carbon atoms, each of which may be represented by a or more groups R ⁴ substituted and wherein one or more CH ₂ groups in the above-mentioned groups may be -R ⁴ C=CR ⁴ -, -C≡C-, Si(R ⁴ ) ₂ , C=O, C=NR ⁴ , -C(=O)O-, -C(=O)NR ⁴ -, NR ⁴ , P(=O)(R ⁴ ), -O-, -S-, SO or SO ₂ substituted , or an aromatic or heteroaromatic ring system having ⁵ to 30 aromatic ring atoms which may be substituted in each case by one or more radicals R4, wherein two or more radicals ^R3 can be linked to each other and may form rings; R ⁴ is identically or differently in each case H, D, F, Cl, Br, I, C(=O)R ⁵ , CN, Si(R ⁵ ) ₃ , N(R ⁵ ) ₂ , P(=O)(R ⁵ ) ₂ , OR ⁵ , S(=O)R ⁵ , S(=O) ₂ R ⁵ , straight-chain alkyl or alkoxy having 1 to 20 carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms or an alkenyl or alkynyl group having ² to 20 carbon atoms, each of which may be substituted by one or more groups R and Wherein one or more CH ₂ groups in the above groups can be replaced by -R ⁵ C=CR ⁵ -, -C≡C-, Si(R ⁵ ) ₂ , C=O, C=NR ⁵ , -C(= O)O-, _-C (=O) ^NR5- , ^NR5 , P(=O)(R5 ⁾ , -O-, -S-, SO or SO2 generation, or an aromatic or heteroaromatic ring system having ⁵ to 30 aromatic ring atoms which may be substituted in each case by one or more radicals R, wherein two or more radicals R ^may be mutually linked and can form a ring; R ⁵ is in each case identically or differently H, D, F or an aliphatic, aromatic or heteroaromatic organic group having 1 to 20 carbon atoms, in addition, one or more of hydrogen atoms can be replaced by D or F; here two or more substituents R can be linked to each other and can form a ring; wherein at least ^one of the two groups Ar must contain ¹⁰ or more aromatics and wherein, if ^one of the two groups Ar1 is ^a phenyl group, the other of the two groups Ar1 must not contain more than 14 aromatic ring atoms.

其中以下適用於所使用之符號和指數： Ar ¹在各自情況下相同或不同地表示具有6至18個芳族環原子之芳基或雜芳基，其於各情況下可被一或多個基團R ¹取代，其中式(1)中之至少一個基團Ar ¹具有10或更多個芳族環原子； Ar ²在各自情況下相同或不同地表示具有6個芳族環原子之芳基或雜芳基，其於各情況下可被一或多個基團R ¹取代； Ar ³、Ar ⁴在各自情況下相同或不同地表示具有5至25個芳族環原子之芳族或雜芳族系統，其於各情況下可被一或多個基團R ¹取代； E 在各自情況下相同或不同地選自-BR ⁰-、-C(R ⁰) ₂-、-C(R ⁰) ₂-C(R ⁰) ₂-、-C(R ⁰) ₂-O-、-C(R ⁰) ₂-S-、-R ⁰C=CR ⁰-、  -R ⁰C=N-、Si(R ⁰) ₂、-Si(R ⁰) ₂-Si(R ⁰) ₂-、-C(=O)-、-C(=NR ⁰)-、-C(=C(R ⁰) ₂)-、-O-、-S-、-S(=O)-、-SO ₂-、-N(R ⁰)-、  -P(R ⁰)-及-P((=O)R ⁰)-，且兩個基團E彼此之間可處於順位或反位； R ⁰、R ¹在各自情況下相同或不同地表示H、D、F、Cl、Br、I、CHO、CN、N(Ar ⁵) ₂、C(=O)Ar ⁵、P(=O)(Ar ⁵) ₂、S(=O)Ar ⁵、S(=O) ₂Ar ⁵、NO ₂、Si(R ²) ₃、B(OR ²) ₂、OSO ₂R ²、各自可被一或多個基團R ²取代的具有1至40個碳原子之直鏈烷基、烷氧基或硫代烷基或具有3至40個碳原子之分支或環狀烷基、烷氧基或硫代烷基，其中在各自情況下一或多個不相鄰之CH ₂基團可被R ²C=CR ²、C≡C、Si(R ²) ₂、Ge(R ²) ₂、Sn(R ²) ₂、C=O、C=S、C=Se、P(=O)(R ²)、SO、SO ₂、O、S或CONR ²取代，且其中一或多個氫原子可被D、F、Cl、Br、I、CN或NO ₂取代、在各自情況下可被一或多個基團R ²取代的具有5至60個芳族環原子之芳族或雜芳族環系統，或可被一或多個基團R ²取代的具有5至40個芳族環原子之芳氧基，其中兩個相鄰取代基R ⁰及/或兩個相鄰取代基R ¹可形成可被一或多個基團R ²取代的單環或多環之脂族環系統或芳族環系統； R ²在各自情況下相同或不同地表示H、D、F、Cl、Br、I、CHO、CN、N(Ar ⁵) ₂、C(=O)Ar ⁵、P(=O)(Ar ⁵) ₂、S(=O)Ar ⁵、S(=O) ₂Ar ⁵、NO ₂、Si(R ³) ₃、B(OR ³) ₂、OSO ₂R ³、各自可被一或多個基團R ³取代的具有1至40個碳原子之直鏈烷基、烷氧基或硫代烷基或具有3至40個碳原子之分支或環狀烷基、烷氧基或硫代烷基，其中在各自情況下一或多個不相鄰之CH ₂基團可被R ³C=CR ³、C≡C、Si(R ³) ₂、Ge(R ³) ₂、Sn(R ³) ₂、C=O、C=S、C=Se、P(=O)R ³、SO、SO ₂、O、S或CONR ³取代，且其中一或多個氫原子可被D、F、Cl、Br、I、CN或NO ₂取代、在各自情況下可被一或多個基團R ³取代的具有5至60個芳族環原子之芳族或雜芳族環系統，或可被一或多個基團R ³取代的具有5至60個芳族環原子之芳氧基，其中兩個相鄰取代基R ²可形成可被一或多個基團R ³取代的單環或多環之脂族環系統或芳族環系統； R ³在各自情況下相同或不同地表示H、D、F、Cl、Br、I、CN、具有1至20個碳原子之直鏈烷基、烷氧基或硫代烷基或具有3至20個碳原子之分支或環狀烷基、烷氧基或硫代烷基，其中在各自情況下一或多個不相鄰之CH ₂基團可被SO、SO ₂、O、S取代，且其中一或多個氫原子可被D、F、Cl、Br或I取代，或具有5至24個碳原子之芳族或雜芳族環系統； Ar ⁵係在各情況下也可被一或多個基團R ³取代的具有5至24個芳族環原子，較佳地5至18個芳族環原子之芳族或雜芳族環系統； n係1至20之整數； 其中若n等於1且基團Ar ³或Ar ⁴中之至少一個表示苯基，則式(1)之化合物帶有至少一個基團R ⁰或R ¹，該至少一個基團R ⁰或R ¹表示各自可被一或多個基團R ²取代的具有2至40個碳原子之直鏈烷基或具有3至40個碳原子之分支或環狀烷基。 Hydrocarbons of the following formula (3) disclosed in other preferred blue fluorescent emission systems PCT/EP2017/066712.

where the following apply to the symbols and indices used: Ar ¹ in each case identically or differently denotes an aryl or heteroaryl radical having 6 to 18 aromatic ring atoms, which in each case may be represented by one or more A group R ¹ is substituted, wherein at least one of the groups Ar ¹ in formula (1) has 10 or more aromatic ring atoms; Ar ² in each case identically or differently represents an aromatic group having 6 aromatic ring atoms radicals or heteroaryl radicals, which in each case may be substituted by one or more radicals R ¹ ; Ar ³ , Ar ⁴ in each case identically or differently represent aromatic or Heteroaromatic systems, which in each case may be substituted by one or more groups R ¹ ; E is in each case identically or differently selected from -BR ⁰ -, -C(R ⁰ ) ₂ -, -C( R ⁰ ) ₂ -C(R ⁰ ) ₂ -, -C(R ⁰ ) ₂ -O-, -C(R ⁰ ) ₂ -S-, -R ⁰ C=CR ⁰ -, -R ⁰ C=N -, Si(R ⁰ ) ₂ , -Si(R ⁰ ) ₂ -Si(R ⁰ ) ₂ -, -C(=O)-, -C(=NR ⁰ )-, -C(=C(R ⁰ ) ₂ )-, -O-, -S-, -S(=O)-, -SO ₂ -, -N(R ⁰ )-, -P(R ⁰ )- and -P((=O)R ⁰ )-, and the two groups E can be in cis-position or trans-position with respect to each other; R ⁰ , R ¹ in each case identically or differently represent H, D, F, Cl, Br, I, CHO, CN, N(Ar ⁵ ) ₂ , C(=O)Ar ⁵ , P(=O)(Ar ⁵ ) ₂ , S(=O)Ar ⁵ , S(=O) ₂ Ar ⁵ , NO ₂ , Si(R ² ) ₃ , B(OR ² ) ₂ , OSO ₂ R ² , straight-chain alkyl, alkoxy or thioalkyl having 1 to 40 carbon atoms, each of which may be substituted by one or more groups R ² , or Branched or cyclic alkyl, alkoxy or thioalkyl having 3 to 40 carbon atoms, wherein in each case or more non-adjacent CH ₂ groups can be replaced by R ² C=CR ² , C≡C, Si(R ² ) ₂ , Ge(R ² ) ₂ , Sn(R ² ) ₂ , C=O, C=S, C=Se, P(=O)(R ² ), SO, SO ₂ , O, S or CONR ² , wherein one or more hydrogen atoms may be substituted by D, F, Cl, Br, I, CN or NO ₂ , in each case by one or more groups R ² A substituted aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms, or an aryloxy group having 5 to 40 aromatic ring atoms which may be substituted by one or more groups R2, ^two of which Two adjacent substituents R ⁰ and/or two adjacent substituents R ¹ may form a monocyclic or polycyclic lipid which may be substituted by one or more groups R ² Aromatic ring systems or aromatic ring systems; R ² in each case identically or differently represents H, D, F, Cl, Br, I, CHO, CN, N(Ar ⁵ ) ₂ , C(=O)Ar ⁵ , P(=O)(Ar ⁵ ) ₂ , S(=O)Ar ⁵ , S(=O) ₂ Ar ⁵ , NO ₂ , Si(R ³ ) ₃ , B(OR ³ ) ₂ , OSO ₂ R ³ , straight-chain alkyl, alkoxy or thioalkyl having 1 to 40 carbon atoms or branched or cyclic alkyl having 3 to 40 carbon atoms, each substituted by one or more groups ^R3 , alkoxy or thioalkyl, wherein in each case one or more non-adjacent CH ₂ groups can be replaced by R ³ C=CR ³ , C≡C, Si(R ³ ) ₂ , Ge(R ³ ) ₂ , Sn(R ³ ) ₂ , C=O, C=S, C=Se, P(=O)R ³ , SO, SO ₂ , O, S or CONR ³ substituted, and one or more of them Aromatic or heterocyclic atoms having ₅ to 60 aromatic ring atoms which may be substituted by D, F, Cl, Br, I, CN or NO2, in each case by one or more groups ^R3 Aromatic ring systems, or aryloxy groups having 5 to 60 aromatic ring atoms which may be substituted by one or more radicals ^R , wherein ^two adjacent substituents R may form radicals which may be substituted by one or more radicals Monocyclic or polycyclic aliphatic or aromatic ring systems substituted by the group R ³ ; R ³ in each case identically or differently represents H, D, F, Cl, Br, I, CN, having 1 to 20 straight-chain alkyl, alkoxy or thioalkyl of 1 carbon atoms or branched or cyclic alkyl, alkoxy or thioalkyl of 3 to 20 carbon atoms, wherein in each case one or more Non-adjacent CH ₂ groups may be substituted with SO, SO ₂ , O, S, and one or more of these hydrogen atoms may be substituted with D, F, Cl, Br, or I, or have 5 to 24 carbon atoms Aromatic or heteroaromatic ring systems; Ar ⁵ has 5 to 24 aromatic ring atoms, preferably 5 to 18 aromatic rings, which may also be substituted in each case by one or more groups R ³ an aromatic or heteroaromatic ring system of atoms; n is an integer from 1 to 20; wherein if n is equal to 1 and at least one of the groups Ar ³ or Ar ⁴ represents a phenyl group, the compounds of formula (1) carry at least A group R ⁰ or R ¹ , the at least one group R ⁰ or R ¹ represents a straight-chain alkyl group having 2 to 40 carbon atoms or a group having 3 to 40 carbon atoms, each of which may be substituted by one or more groups R ² A branched or cyclic alkyl group of one carbon atom.

Preferred compounds useful as phosphorescent emitters are described below by way of example.

WO 00/70655, WO 01/41512, WO 02/02714, WO 02/15645, EP 1191613, EP 1191612, EP 1191614 and WO 2005/033244 disclose examples of phosphorescent emitters. In general, all phosphorescent complexes known to those skilled in the art for use in phosphorescent OLEDs and organic electroluminescence from the prior art are suitable, and those skilled in the art can use other phosphorescent complexes to obtain Not progressive.

The phosphorescent metal complex preferably contains Ir, Ru, Pd, Pt, Os or Re, more preferably Ir.

The preferred ligands are 2-phenylpyridine derivatives, 7,8-benzoquinoline derivatives, 2-(2-thienyl)pyridine derivatives, 2-(1-naphthyl)pyridine derivatives, 1 - Phenylisoquinoline derivatives, 3-phenylisoquinoline derivatives or 2-phenylquinoline derivatives. All of these compounds can be substituted, for example with fluorine, cyano and/or trifluoromethyl substituents to obtain the blue color. The auxiliary ligand is preferably acetylpyruvate or picolinic acid.

In particular, complexes of Pt or Pd with a tetradentate ligand of formula EM-16 are suitable.

The compound of formula EM-16 is described in more detail in US 2007/0087219 A1, wherein for the explanation of the substituents and indices in the above formula, this specification is cited for the purpose of disclosure. In addition, Pt-porphyrin complexes with enlarged ring systems (US 2009/0061681 A1) and Ir complexes such as 2,3,7,8,12,13,17,18-octaethyl-21H , 23H-porphyrin-Pt(II), tetraphenyl-Pt(II) tetrabenzoporphyrin (US 2009/0061681 A1), cis-bis( ² -phenylpyridine-N,C2')Pt (II), cis-bis(2-(2'-thienyl)pyridine-N,C ³ ')Pt(II), cis-bis(2-(2'-thienyl)quinoline-N, C ⁵ ')Pt(II), (acetylpyruvic acid)(2-(4,6-difluorophenyl)pyridine-N,C ² ')Pt(II) or gins(2-phenylpyridine- N,C ² ')Ir(III) (= Ir(ppy) ₃ , green), (acetylpyruvate)bis(2-phenylpyridine-N,C ² )Ir(III) (= Ir( ppy) ₂ acetylpyruvate, green, US 2001/0053462 A1, Baldo, Thompson et al., Nature 403, (2000), 750-753), bis(1-isoquinoline-N, ^C2 ') ( ² -phenylpyridine-N,C2')iridium(III), bis( ² -phenylpyridine-N,C2')(1-phenylisoquinoline-N, ^C2 ')iridium(III) ), (acetylpyruvate)bis(2-(2'-benzothienyl)pyridine-N,C3')iridium( ^III ), (picolinic acid)bis(2-(4',6'- Difluorophenyl)pyridine-N, ^C2 ')iridium(III) (FIrpic, blue), (4(1-pyrazolyl)boronic acid)bis(2-(4',6'-difluorophenyl) ) pyridine-N,C ² ')Ir(III), ginseng (2-(biphenyl-3-yl)-4-tert-butylpyridine)iridium(III), (ppz) ₂ Ir(5phdpym) (US 2009/0061681 A1), (45ooppz) ₂ -Ir(5phdpym) (US 2009/0061681 A1); 2-phenylpyridine derivatives-Ir complexes, for example, PQIr(=bis(2-phenylquinoline- N,C ² ')Acetylpyruvate)Iridium(III), gins(2-phenylisoquinoline-N,C)Ir(III) (red), (Acetylpyruvate)bis(2- (2'-Benzo[4,5-a]thienyl)pyridine _- N,C3)Ir ([ ^Btp2Ir (acac)] (red), Adachi et al., Appl. Phys. Lett . 78 (2001 ), 1622-1624).

Also suitable are complexes of trivalent lanthanides, such as Tb ³⁺ and Eu ³⁺ (J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657 , 1990, US 2007/0252517 A1) or phosphorescent complexes of Pt(II), Ir(I), Rh(I) and maleonitrile dithiolate (Johnson et al., JACS 105, 1983, 1795), Re(I) tricarbonyldiimine complexes (Wrighton, JACS 96, 1974, 998, other than others), Os(II) complexes containing cyano ligands and bipyridine or phenanthroline ligands ( Ma et al, Synth. Metals 94, 1998, 245).

Other phosphorescent emitters with tridentate ligands are described in US 6824895 and US 10/729238. Red emitting phosphorescent complexes are found in US 6835469 and US 6830828.

Particularly preferred compounds for use as phosphorescent dopants are especially those of the formula EM- described in US 2001/0053462 A1 and Inorg. Chem. Compounds of 17 and derivatives thereof.

Derivatives are described in US 7378162 B2, US 6835469 B2 and JP 2003/253145 A.

In addition, the compounds of the formulae EM-18 to EM-21 as described in US 7238437 B2, US 2009/008607 A1 and EP 1348711 and their derivatives can be used as emitters.

Quantum dots can also be used as emitters, these materials are disclosed in detail in WO 2011/076314 A1.

Compounds used as host materials, particularly with light-emitting compounds, include materials from a wide variety of species.

The host material typically has a larger band gap between the HOMO and LUMO than the emitter material used. In addition, preferred host materials exhibit the properties of a hole or electron transport material. Furthermore, the host material may have both electron and hole transport properties.

In some cases, the host material is also referred to as the host material, especially if the host material is used in conjunction with a phosphorescent emitter in an OLED.

Preferred host materials or co-host materials, especially for use with fluorescent dopants, are selected from the following classes: oligoarylenes (eg according to EP 676461-2,2',7 ,7'-tetraphenylspirobispyridine or dinaphthylanthracene), especially oligomeric arylidene groups containing fused aromatic groups, such as, for example, anthracene, benzanthracene, triphenylene (DE 10 2009 005746 , WO 2009/069566), phenanthrene, condensed tetraphenyl, columbine, chrysene, fenugreek, spiro fen, perylene, phthaloperylene, naphthalene, decacyclene, redfluorene; oligomeric extension Aryl vinylidene (eg DPVBi=4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl or spiro-DPVBi according to EP 676461); polypodal metal complexes ( polypodal metal complex) (for example according to WO 04/081017), especially metal complexes of 8-hydroxyquinoline, for example AlQ ₃ (= cf(8-hydroxyquinoline)aluminum(III) or bis(2-methyl) -8-quinoline)-4-(phenylfenolinyl)aluminum; also imidazole chelates (US 2007/0092753 A1) and quinoline-metal complexes; aminoquinoline metal complexes; benzene quinoline metal complexes; hole-conducting compounds (for example according to WO 2004/058911); electron-conducting compounds, especially ketones, phosphine oxides, thionite and the like (for example according to WO 2005/084081 and WO 2005/084082); atropisomers (eg according to WO 2006/048268); boronic acid derivatives (eg according to WO 2006/117052) or benzanthracenes (eg according to WO 2008/145239).

Particularly preferred compounds that can be used as host materials or co-host materials are selected from the following classes: oligomeric arylenes, including anthracene, benzanthracene and/or pyrene, or atropisomers of these compounds. Oligomeric arylidene groups in the sense of the present invention are intended to mean compounds in which at least three aryl groups or arylidene groups are bonded to each other.

其中Ar ⁴、Ar ⁵、Ar ⁶在各自情況下相同或不同地為可視需要地被取代的具有5至30個芳族環原子之芳基或雜芳基，且p代表1至5之整數；若p=1時Ar ⁴、Ar ⁵和Ar ⁶中π電子之總和為至少30個，且若p=2時為至少36個，且若p=3時為至少42個。 Preferred host materials are especially selected from compounds of formula (H-1):

wherein Ar ⁴ , Ar ⁵ , Ar ⁶ are identically or differently in each case an optionally substituted aryl or heteroaryl group having 5 to 30 aromatic ring atoms, and p represents an integer from 1 to 5; The sum of pi electrons in Ar ⁴ , Ar ⁵ and Ar ⁶ is at least 30 if p=1, at least 36 if p=2, and at least 42 if p=3.

In the compound of formula (H-1), the group Ar ⁵ particularly preferably represents anthracene, and the groups Ar ⁴ and Ar ⁶ are bonded to the 9- and 10-positions, wherein these groups are optionally substituted. Very particularly preferably, at least one of the groups Ar ⁴ and/or Ar ⁶ is selected from 1- or 2-naphthyl, 2-, 3- or 9-phenanthryl or 2-, 3-, 4-, Fused aryl of 5-, 6- or 7-benzoanthryl. Anthracene compounds, such as 2-(4-methylphenyl)-9,10-bis(2-naphthyl)anthracene, 9-(2-naphthyl), are described in US 2007/0092753 A1 and US 2007/0252517 A1 )-10-(1,1'-biphenyl)anthracene and 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene, 9,10-diphenylanthracene, 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene , 10-bis (phenylethynyl) anthracene and 1,4-bis (9'-ethynyl anthracenyl) benzene. Also preferred are compounds containing two anthracene units (US 2008/0193796 A1), such as 10,10'-bis[1,1',4',1'']bitriphenyl-2-yl-9,9 '-Dianthracene.

More preferred compounds are derivatives of aromatic amines, styrylamines, fluorescein, diphenylbutadiene, tetraphenylbutadiene, cyclopentadiene, tetraphenylcyclopentadiene, pentaphenyl Phenylcyclopentadiene, coumarin, oxadiazole, dibenzoxazoline (bisbenzothiazole), oxazole, pyridine, pyrazine, imine, benzothiazole, benzoxazole, benzene Zimidazoles (US 2007/0092753 A1) such as 2,2',2''-(1,3,5-phenylene) sham[1-phenyl-1H-benzimidazole], aldazine, Styrene, styryl derivatives such as 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene and stilbene derivatives (US 5121029), diphenylethylene, vinylanthracene, Diaminocarbazole, pyran, thiopyran, diketopyrrolopyrrole, polymethyne, cinnamate and fluorescent dyes.

Particularly preferred are derivatives of arylamines and styrylamines, such as TNB (=4,4'-bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl). Metal-oxinoid complexes such as LiQ or AlQ ₃ can be used as co-hosts.

The preferred compounds based on oligomeric arylidene groups are disclosed in US 2003/0027016 A1, US 7326371 B2, US 2006/043858 A, WO 2007/114358, WO 2008/145239, JP 3148176 B2, EP 1009044, US 2004 /018383, WO 2005/061656 A1, EP 0681019B1, WO 2004/013073A1, US 5077142, WO 2007/065678 and DE 102009005746, of which particularly preferred compounds are described by formulae H-2 to H-8.

Furthermore, compounds useful as hosts or hosts include materials used with phosphorescent emitters.

These compounds which can also be used as polymer structural elements include CBP (N,N-biscarbazolylbiphenyl), carbazole derivatives (eg according to WO 2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO 2008/086851), azacarbazoles (eg according to EP 1617710, EP 1617711, EP 1731584 or JP 2005/347160), ketones (eg according to WO 2004/093207 or according to DE 102008033943), phosphine oxides, Silane and bismuth (eg according to WO 2005/003253), oligomeric phenylenes, aromatic amines (eg according to US 2005/0069729), bipolar matrix materials (eg according to WO 2007/137725), silanes (eg according to WO 2005/111172) ), 9,9-diarylperylene derivatives (for example according to DE 102008017591), azaborane or boronate esters (for example according to WO 2006/117052), triazine derivatives (for example according to DE 102008036982), indium Indocarbazole derivatives (for example according to WO 2007/063754 or WO 2008/056746), indenocarbazole derivatives (for example according to DE 102009023155 and DE 102009031021), diazepine derivatives (for example according to DE 102009022858), triazole derivatives, oxazole and oxazole derivatives, imidazole derivatives, polyarylene derivatives, pyrazoline derivatives, pyrazolone derivatives, distyrylpyrazine derivatives, Thiopyran dioxide derivatives, phenylenediamine derivatives, tertiary aromatic amines, styrylamines, chalcone derivatives substituted with amino groups, indole, hydrazone derivatives, stilbene derivatives, Metal complexes of silazane derivatives, aromatic dimethylene compounds, carbodiimide derivatives, 8-hydroxyquinoline derivatives, such as, for example, _AlQ3 (which may also contain triarylaminophenol ligands) Seat (US 2007/0134514 A1)), metal complexes/polysilane compounds and thiophene, benzothiophene and dibenzothiophene derivatives.

An example of a preferred carbazole derivative is mCP (=1,3-N,N-bis-carbazolylbenzene (=9,9'-(1,3-phenylene)bis(9H-carbazole)) (Formula H-9), CDBP (=9,9'-(2,2'-dimethyl[1,1'-biphenyl]-4,4'-diyl)bis-9H-carbazole), 1,3-bis(N,N'-dicarbazolyl)benzene (=1,3-bis(carbazol-9-yl)benzene), PVK (polyvinylcarbazole), 3,5-bis(9H) -carbazol-9-yl)biphenyl and CMTTP (formula H-10). Particularly preferred compounds are disclosed in US 2007/0128467 A1 and US 2005/0249976 A1 (formula H-11 and H-13).

Preferred tetraaryl silicon compounds are disclosed, for example, in US 2004/0209115, US 2004/0209116, US 2007/0087219 A1 and H. Gilman, E.A. Zuech, Chemistry & Industry (London, United Kingdom), 1960, 120.

Particularly preferred tetraarylsilicon compounds are described by formulae H-14 to H-21.

Group 4 of particularly preferred compounds for the preparation of phosphorescent dopants are disclosed in particular in DE 102009022858, DE 102009023155, EP 652273 B1, WO 2007/063754 and WO 2008/056746, wherein particularly preferred compounds are of the formulae H-22 to H-25 description.

Regarding the functional compounds which can be used according to the invention and which can be used as host materials, substances containing at least one nitrogen atom are particularly preferred. These preferably include aromatic amines, triazine derivatives and carbazole derivatives. Therefore, carbazole derivatives in particular exhibit surprisingly high efficiency. Triazine derivatives lead to unexpectedly long lifetimes of electronic devices.

A variety of different matrix materials in mixtures, in particular at least one electron-conducting matrix material and at least one hole-conducting matrix material, can also preferably be used. It is also preferred to use a mixture of a charge transporting matrix material and an electrically inert matrix material, which mixture is largely not involved in charge transport, if at all, as described for example in WO 2010/108579.

Furthermore, compounds that improve the transition from singlet to triplet state and are used to support functional compounds with emitter properties can be used to improve the phosphorescent properties of these compounds. Suitable for this purpose are in particular carbazole and bridged carbazole dimer units as described, for example, in WO 2004/070772 A2 and WO 2004/113468 A1. Also suitable for this purpose are ketones, phosphine oxides, selenium, sine, silane derivatives and similar compounds as described, for example, in WO 2005/040302 A1.

The n-dopant here means a reducing agent, ie an electron donor. Preferred examples of n-dopants are W(hpp) ₄ and other electron-rich metal complexes according to WO 2005/086251 A2, P=N compounds (eg WO 2012/175535 A1, WO 2012/175219 A1), Naphthylene carbodiimide (eg WO 2012/168358 A1), pyridine (eg WO 2012/031735 A1), radicals and diradicals (eg EP 1837926 A1, WO 2007/107306 A1), pyridine (eg EP 2452946 A1, EP 2463927 A1), N-heterocyclic compounds (eg WO 2009/000237 A1) and acridines and phenazines (eg US 2007/145355 A1).

Furthermore, the formulations may include wide bandgap materials as functional materials. By wide bandgap material is meant a material in the sense of the disclosure of US 7,294,849. These systems exhibit particularly favorable performance data in electroluminescent devices.

The compound used as the wide band gap material may preferably have a band gap of 2.5 eV or higher, preferably 3.0 eV or higher, particularly preferably 3.5 eV or higher. The band gap can be calculated in particular from the energy levels of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).

Furthermore, the formulation may include a hole blocking material (HBM) as a functional material. By hole blocking material is meant a material that prevents or minimizes the transport of holes (positive charges) in a multilayer system, especially if the material is arranged in a layer adjacent to an emissive or hole conducting layer. In general, the HOMO level of the hole blocking material is lower than the hole transport material of the adjacent layer. The hole blocking layer is often disposed between the light emitting layer and the electron transport layer of the OLED.

Essentially any known hole blocking material can be used. In addition to other hole blocking materials described elsewhere in this case, advantageous hole blocking materials are metal complexes (US 2003/0068528) such as bis(2-methyl-8-quinoline) (4 - Phenylphenol)aluminum(III) (BAlQ). The facula-para(1-phenylpyrazole-N,C2)iridium(III) (Ir(ppz) ₃ ) is also used for this purpose (US 2003/0175553 A1). Phasphaline derivatives such as BCP or phthalimides such as TMPP can also be used.

Furthermore, advantageous hole blocking materials are described in WO 00/70655 A2, WO 01/41512 and WO 01/93642 A1.

Furthermore, the formulations may include electron blocking materials (EBMs) as functional materials. By electron blocking material is meant a material that prevents or minimizes the transport of electrons in a multilayer system, especially if the material is arranged in the form of a layer adjacent to an emissive layer or an electron conducting layer. In general, the LUMO energy level of the electron blocking material is higher than that of the electron transport material of the adjacent layer.

Basically any known electron blocking material can be used. In addition to other electron blocking materials described elsewhere in this case, advantageous electron blocking materials are transition metal complexes such as Ir(ppz) ₃ (US 2003/‌0175553).

The electron blocking material can preferably be selected from amines, triarylamines and derivatives thereof.

In addition, functional compounds that can be used as organic functional materials in formulations, if low molecular weight compounds, preferably have ≤3000 g/mol, more preferably ≤2000 g/mol, most preferably ≤1,000 g/mol molecular weight.

Also of particular interest are functional compounds, which are characterized by high glass transition temperatures. In this regard, particularly preferred functional compounds that can be used as organic functional materials in formulations are glass transition temperatures ≥ 70°C, preferably ≥ 100° C, more preferably ≥ 125° C, optimally determined according to DIN 51005 Those functional compounds above ≥150°C.

The formulations may also contain polymers as organic functional materials. The above-mentioned compounds as organic functional materials generally have relatively low molecular weights and can also be mixed with polymers. These compounds can also be covalently incorporated into polymers. This is particularly useful with compounds substituted with reactive leaving groups such as bromine, iodine, chlorine, boronic acids or boronic esters, or with reactive polymerizable groups such as olefins or oxetanes. These can be used as monomers for the production of corresponding oligomers, dendrimers or polymers. The oligomerization or polymerization here preferably occurs via halogen functionality or boronic acid functionality or via polymerizable groups. Furthermore, polymers can be crosslinked via groups of this type. The compounds and polymers according to the invention can be used in crosslinked or uncrosslinked layers.

Polymers that can be used as organic functional materials often contain units or structural elements that have been described in the context of the above-mentioned compounds, in particular as disclosed in WO 02/077060 A1, WO 2005/014689 A2 and WO 2011/076314 A1. Those listed extensively. These are incorporated by reference into this case. For example, functional materials can come from the following categories: Group 1: Structural elements capable of producing hole injection and/or hole transport properties; Group 2: Structural elements capable of producing electron injection and/or electron transport properties; Group 3: Structural elements combining the properties described in Groups 1 and 2; Group 4: Structural elements with luminescent properties, especially phosphorescent groups; Group 5: Structural elements for improving the transition from the so-called singlet to triplet state; Group 6: Structural elements affecting the morphology or luminescent colour of the resulting polymers; Group 7: Structural elements commonly used as skeletons.

Structural elements here can also have different functions, so an explicit assignment is not necessarily advantageous. For example, the structural elements of group 1 can also be used as skeletons.

The polymer having hole transport or hole injection properties used as an organic functional material contains a structural element from Group 1, and preferably may contain a unit corresponding to the above hole transport or hole injection material.

Other preferred structural elements of group 1 are, for example, triarylamines, benzidines, tetraaryl-p-phenylenediamines, carbazoles, azulene, thiophenes, pyrroles and furans and their derivatives and other O-containing compounds with high HOMO , S- or N-heterocycle. These aromatic amines and heterocycles preferably have HOMOs higher than -5.8 eV (relative to the vacuum level), particularly preferably higher than -5.5 eV.

其中各符號具有以下含義： Ar ¹對於不同之重複單元，在各自情況下相同或不同地為單鍵或單環或多環芳基，其可視需要地經取代； Ar ²對於不同之重複單元，在各自情況下相同或不同地為單環或多環芳基，其可視需要地經取代； Ar ³對於不同之重複單元，在各自情況下相同或不同地為單環或多環芳基，其可視需要地經取代； m         係1、2或3。 Especially preferred are polymers with hole transport or hole injection properties, which contain at least one repeating unit of the following formula HTP-1:

Wherein each symbol has the following meanings: Ar ¹ for different repeating units, in each case identically or differently, is a single bond or a monocyclic or polycyclic aryl group, which may be optionally substituted; Ar ² for different repeating units, In each case, identically or differently, a monocyclic or polycyclic aryl group, which may be optionally substituted; Ar ³ for different repeating units, identically or differently in each case, is a monocyclic or polycyclic aryl group, which Optionally substituted; m is 1, 2 or 3.

其中各符號具有以下含義： R ^a在各自情況下相同或不同地為H、經取代或未經取代之芳族或雜芳族基團、烷基、環烷基、烷氧基、芳烷基、芳氧基、芳硫基、烷氧基羰基、甲矽烷基或羧基、鹵素原子、氰基、硝基或羥基； r    係0、1、2、3或4，且 s    係0、1、2、3、4或5。 Particularly preferred are repeating units of formula HTP-1 selected from the group consisting of units of formula HTP-1A to HTP-1C:

where the symbols have the following meanings: R ^a is in each case, identically or differently, H, a substituted or unsubstituted aromatic or heteroaromatic group, an alkyl group, a cycloalkyl group, an alkoxy group, an aralkyl group , aryloxy, arylthio, alkoxycarbonyl, silyl or carboxyl, halogen atom, cyano, nitro or hydroxyl; r is 0, 1, 2, 3 or 4, and s is 0, 1, 2, 3, 4 or 5.

其中各符號具有以下含義： T ¹和T ²係獨立地選自噻吩、硒吩、噻吩并[2,3-b]噻吩、噻吩并[3,2-b]噻吩、二噻吩并噻吩、吡咯及苯胺，其中這些基團可被一或多個基團R ^b取代； R ^b在各自情況下係獨立地選自鹵素、-CN、-NC、-NCO、-NCS、-OCN、-SCN、-C(=O)NR ⁰R ⁰⁰、-C(=O)X、-C(=O)R ⁰、-NH ₂、‑NR ⁰R ⁰⁰、-SH、-SR ⁰、-SO ₃H、-SO ₂R ⁰、-OH、-NO ₂、-CF ₃、-SF ₅、具有1至40個碳原子的視需要地經取代之甲矽烷基、羰基或烴基，其可視需要地被取代並可視需要地含有一或多個雜原子； R ⁰和R ⁰⁰係各自獨立地為H或具有1至40個碳原子的視需要地經取代之羰基或烴基，其可視需要地被取代並可視需要地含有一或多個雜原子； Ar ⁷和Ar ⁸彼此獨立地表示單環或多環芳基或雜芳基，其可視需要地被取代並可視需要地鍵合於一或兩個相鄰噻吩基或硒吩基之2,3-位； c和e彼此獨立地為0、1、2、3或4，其中1＜c+e≦6； d和f彼此獨立地為0、1、2、3或4。 Especially preferred are polymers with hole transport or hole injection properties, which contain at least one repeating unit of the formula HTP-2:

wherein each symbol has the following meanings: T1 and T2 are independently selected from thiophene, selenophene, thieno[2,3 ^- b]thiophene, thieno[3,2 ^- b]thiophene, dithienothiophene, pyrrole and aniline, wherein these groups may be substituted by one or more groups R ^b ; R ^b in each case is independently selected from halogen, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -C(=O)NR ⁰ R ⁰⁰ , -C(=O)X, -C(=O)R ⁰ , -NH ₂ , -NR ⁰ R ⁰⁰ , -SH, -SR ⁰ , -SO ₃ H, -SO ₂ R ⁰ , -OH, -NO ₂ , -CF ₃ , -SF ₅ , optionally substituted silyl group, carbonyl group or hydrocarbyl group having 1 to 40 carbon atoms, which is optionally substituted and Optionally contain one or more heteroatoms; R ⁰ and R ⁰⁰ are each independently H or an optionally substituted carbonyl or hydrocarbyl group having 1 to 40 carbon atoms, which is optionally substituted and optionally contains one or more heteroatoms; Ar ⁷ and Ar ⁸ independently of each other represent a monocyclic or polycyclic aryl or heteroaryl group, which is optionally substituted and optionally bonded to one or two adjacent thiophenes 2,3-position of the radical or selenophenyl; c and e independently of each other are 0, 1, 2, 3 or 4, wherein 1<c+e≦6; d and f are independently 0, 1, 2 , 3 or 4.

Preferred examples of polymers with hole transport or hole injection properties are described in particular in WO 2007/131582 A1 and WO 2008/009343 A1.

The polymer having electron injection and/or electron transport properties used as an organic functional material contains a structural element from Group 2, preferably a unit corresponding to the above electron injection and/or electron transport material.

Other preferred Group 2 structural elements with electron injection and/or electron transport properties are derived from, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoline and phenazine and their derivatives, and also There are triarylboranes or other O-, S- or N- containing heterocycles with low LUMO levels. These Group 2 structural elements preferably have LUMOs below -2.7 eV (relative to the vacuum level), particularly preferably below -2.8 eV.

The organic functional material may preferably be a polymer containing structural elements of Group 3, in which structural elements that improve hole and electron mobility (ie, structural elements of Groups 1 and 2) are directly connected to each other. Some of these structural elements can be used here as emitters, where the emission color may change, for example to green, red or yellow. Thus, its use is advantageous, for example, for initially blue-emitting polymers to generate other emission colors or broadband emission.

The polymer having light-emitting properties used as an organic functional material contains a structural element of Group 4, and may preferably contain a unit corresponding to the above-mentioned emitter material. Preferred here are polymers containing phosphorescent groups, especially the above-mentioned luminescent metal complexes containing corresponding units containing elements of groups 8 to 10 (Ru, Os, Rh, Ir, Pd, Pt).

Polymers used as organic functional materials containing units of group 5 that improve the transition from the so-called singlet state to triplet state can preferably be used in carriers for phosphorescent compounds, preferably the polymers contain the above-mentioned group 4 the structural element. A polymeric triplet matrix can be used here.

Suitable for this purpose are in particular carbazoles and linked carbazole dimer units as described, for example, in DE 10304819 A1 and DE 10328627 A1. Also suitable for this purpose are ketones, phosphine oxides, sulfites, sine and silane derivatives and similar compounds as described, for example, in DE 10349033 A1. Furthermore, preferred building blocks can be derived from the compounds described above in relation to host materials for use with phosphorescent compounds.

Other organic functional materials are preferably polymers containing Group 6 units that affect the morphology and/or emission color of the polymer. In addition to the polymers mentioned above, these are those polymers having at least one other aromatic or other conjugated structure not included in the aforementioned groups. Therefore, these groups have little or no effect on charge-carrier mobility, non-organometallic complexes, or singlet-triplet transitions.

Structural units of this type can influence the morphology and/or emission color of the resulting polymer. Depending on the structural unit, these polymers can thus also be used as emitters.

In the case of fluorescent OLEDs, therefore, preference is given to aromatic structural elements having 6 to 40 carbon atoms or also tolan, stilbene or bis-styrylarylene derived units , each of which may be substituted with one or more groups. Particular preference is given here to the use of derivatives derived from 1,4-phenylene, 1,4-naphthylene, 1,4- or 9,10-pyrene, 1,6-, 2,7- or 4,9- Pyrene, 3,9- or 3,10-perylene, 4,4'-biphenyl, 4,4"-terphenyl, 4,4'-bis-1,1'-naphthylene, 4,4'- A group of a diphenylacetylene, 4,4'-distyryl or 4,4''-distyryl arylidene derivative.

The polymer used as the organic functional material preferably contains a Group 7 unit, which preferably contains an aromatic structure having 6 to 40 carbon atoms which is often used as a skeleton.

These include in particular 4,5-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives, perylene derivatives disclosed for example in US 5962631, WO 2006/052457 A2 and WO 2006/118345 A1, 9,9-spirobisyl derivatives disclosed in eg WO 2003/020790 A1, 9,10-phenanthrene derivatives disclosed eg in WO 2005/104264 A1, 9,10-diphenyl derivatives disclosed eg in WO 2005/014689 A2 Hydrophenanthrene derivatives, 5,7-dihydrodibenzoxepine derivatives and cis- and trans-indenoindenine derivatives disclosed for example in WO 2004/041901 A1 and WO 2004/113412 A2 and Binaphthyl derivatives disclosed for example in WO 2006/063852 A1, and others disclosed in, for example, WO 2005/056633 A1, EP 1344788 A1, WO 2007/043495 A1, WO 2005/033174 A1, WO 2003/099901 A1 and DE 102006003710 unit.

Particularly preferred are the 7-group structural units selected from the pyrene derivatives disclosed for example in US 5,962,631, WO 2006/052457 A2 and WO 2006/118345 A1, the spirobiphenyl derivatives disclosed for example in WO 2003/020790 A1, benzophene , dibenzophene, benzothiophene and dibenzophene groups and derivatives thereof as disclosed for example in WO 2005/056633 A1, EP 1344788 A1 and WO 2007/043495 A1.

In order to practice the present invention, polymers containing more than one of the above-mentioned Group 1 to 7 structural elements are preferred. Furthermore, it can be provided that the polymer preferably contains more than one structural element from the above-mentioned family, ie a mixture comprising structural elements selected from one family.

Particularly preferred are the following polymers, which in addition to at least one structural element (group 4) having a luminescent property, preferably at least one phosphorescent group, further contain at least one other group 1 to 3, 5 or 6 above Structural elements, wherein these are preferably selected from groups 1 to 3.

If families are present in the polymer, the ratios can be within wide ranges, where these are known to those skilled in the art. If a class of structural elements selected in each case from the above-mentioned groups 1 to 7 is present in the polymer, the proportion is preferably in each case ≥ 5 mol %, particularly preferably in each case ≥ 10 mol % , surprising advantages can be achieved.

The preparation of white light-emitting copolymers is described in detail in particular in DE 10343606 A1.

In order to improve solubility, the polymers may contain corresponding groups. The polymers can preferably be specified to contain substituents such that each repeating unit has an average of at least 2 non-aromatic carbon atoms, particularly preferably at least 4, and particularly preferably at least 8 non-aromatic carbon atoms, with an average of at least 8 non-aromatic carbon atoms present. Values are related to the numerical mean. Individual carbon atoms can be replaced by O or S here, for example. However, a certain proportion, optionally all of the repeating units, may be free of substituents containing non-aromatic carbon atoms. Short-chain substituents are preferred here, since long-chain substituents can adversely affect layers obtained using organic functional materials. Substituents preferably contain up to 12 carbon atoms in a straight chain, preferably up to 8 carbon atoms, particularly preferably up to 6 carbon atoms.

The polymers used as organic functional materials according to the present invention may be in the form of random, alternating or regioregular copolymers, block copolymers or combinations of these copolymers.

In another embodiment, the polymer used as the organic functional material may be a non-conjugated polymer having side chains, wherein this embodiment is particularly important for polymer-based phosphorescent OLEDs. In general, phosphorescent polymers can be obtained by free-radical copolymerization of vinyl compounds, wherein these vinyl compounds contain at least one unit with a phosphorescent emitter and/or at least one charge transport unit, as described in particular in US 7250226 B2 revealed in. Other phosphorescent polymers are described in particular in JP 2007/211243 A2, JP 2007/197574 A2, US 7250226 B2 and JP 2007/059939 A.

In another preferred embodiment, the non-conjugated polymer contains backbone units interconnected by spacer units. Examples of non-conjugated polymer-based triplet emitters based on backbone units are disclosed, for example, in DE 102009023154.

In another preferred embodiment, the non-conjugated polymer can be designed as a fluorescent emitter. Preferred non-conjugated polymers with side chains are fluorescent emitters containing anthracene or benzanthracene groups or derivatives of these groups in the side chains, wherein these polymers are disclosed, for example, in JP 2005/108556 , JP 2005/285661 and JP 2003/338375.

These polymers are often useful as electron- or hole-transport materials, wherein these polymers are preferably designed as non-conjugated polymers.

Furthermore, the functional compound used as the organic functional material in the formulation preferably has a molecular weight _Mw of ≧10,000 g/mol, particularly preferably ≧20,000 g/mol, especially preferably ≧40,000 g/mol.

The molecular weight M _w of this polymer is preferably in the range from 10,000 to 2,000,000 g/mol, particularly preferably in the range from 20,000 to 1,000,000 g/mol and very particularly preferably in the range from 40,000 to 300,000 g/mol . The molecular weight _Mw is determined by GPC (=gel permeation chromatography) against a polystyrene internal standard.

The publications cited above to describe functional compounds are incorporated herein by reference for the purpose of disclosure.

Formulations according to the present invention may contain all organic functional materials necessary for the manufacture of individual functional layers of electronic devices. For example, if the hole transport, hole injection, electron transport or electron injection layer is explicitly composed of a functional compound, the formulation specifically includes this compound as the organic functional material. If the emissive layer comprises, for example, a combination of an emitter and a host or host material, the formulation expressly comprises a mixture of the emitter and the host or host material as the organic functional material, as described in more detail elsewhere in this document.

In addition to the aforementioned components, the formulations according to the invention may also further comprise additives and processing aids. These include, inter alia, surface-active substances (surfactants), lubricants and greases, additives to modify viscosity, additives to increase conductivity, dispersants, hydrophobic agents, adhesion promoters, flow improvers, defoamers, defoamers Aerosols, diluents which may be reactive or non-reactive, fillers, auxiliaries, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors.

The present invention further relates to a method for the preparation of the formulation according to the present invention, wherein at least one organic functional material useful for the production of functional layers of electronic devices is mixed with three different organic solvents A, B and C.

The formulations according to the present invention can be used to make layer or multilayer structures with organic functional materials in layers, which is required for the manufacture of preferred electronic or optoelectronic components such as OLEDs.

The formulations of the present invention are preferably used to form a functional layer on a substrate or one of the layers applied to a substrate. The substrate may or may not have a bank structure.

The present invention also relates to an electronic device, preferably a method for the preparation of an electroluminescent device, wherein the formulation according to the present invention is deposited, preferably printed, more preferably inkjet printed, on a surface and subsequently dried to prepare an electronic device device, preferably at least one layer of an electroluminescent device.

The functional layer can be produced, for example, by flood coating, dip coating, spray coating, spin coating, screen printing, letterpress printing, gravure printing, rotary printing, roll coating, flexographic printing, offset printing or nozzle printing, preferably is inkjet printed on the substrate or on one of the layers applied to the substrate.

After the formulation according to the invention has been applied to the substrate or the applied functional layer, a drying step can be carried out to remove the solvent from the aforementioned continuous phase. Drying can preferably be performed at relatively low temperatures and for relatively long periods of time to avoid bubble formation and to obtain a uniform coating. Drying can preferably be performed at a temperature in the range of 80 to 300°C, more preferably 150 to 250°C, and most preferably 160 to 200°C. Drying here may preferably be at a pressure in the range from ^10-6 mbar to 2 bar, more preferably in the range from ^10-2 mbar to 1 bar, and most preferably in the range from ^10-1 mbar to 100 mbar proceed below. During the drying process, the temperature of the substrate may vary from -15°C to 250°C. The duration of drying depends on the degree of drying to be achieved, in which small amounts of water can be removed if desired at relatively high temperatures in conjunction with preferably performed sintering.

Furthermore, the process may be repeated several times to form different or the same functional layers. Here, crosslinking of the functional layer formed can be carried out to prevent its dissolution, as disclosed, for example, in EP 0637899 A1.

The present invention also relates to electronic devices obtainable by a process for manufacturing electronic devices.

The invention also relates to an electronic device, preferably an electroluminescent device, characterized in that the formulation according to the invention is deposited, preferably printed, more preferably inkjet printed, on a surface and subsequently dried to produce at least one layer .

The present invention also relates to an electronic device having at least one functional layer comprising at least one organic functional material obtainable by the above-mentioned method for manufacturing an electronic device.

By electronic device is meant a device comprising an anode, a cathode and at least one functional layer therebetween, wherein the functional layer comprises at least one organic compound or organometallic compound.

The organic electronic device is preferably an organic electroluminescent device (OLED), a polymer electroluminescent device (PLED), an organic integrated circuit (O-IC), an organic field effect transistor (O-FET), an organic thin film transistor (O-TFT), organic light-emitting transistors (O-integrated LET), organic solar cells (O-SC), organic photovoltaic (OPV) cells, organic optical detectors, organic photoreceptors, organic field quenching devices (O -FQDs), organic electrical sensors, light emitting electrochemical cells (LECs) or organic laser diodes (O-lasers), more preferably organic electroluminescent devices (OLEDs) or polymer electroluminescent devices (PLEDs).

Active components are generally organic or inorganic materials added between the anode and cathode, where these active components affect, maintain and/or improve the properties of electronic devices, such as their performance and/or lifetime, such as charge injection, charge transport or Charge blocking materials, but especially emissive and host materials. Therefore, the organic functional material that can be used to manufacture the functional layer of the electronic device preferably contains the active component of the electronic device.

An organic electroluminescent device is a preferred embodiment of the present invention. The organic electroluminescent device includes a cathode, an anode and at least one light-emitting layer.

It is also preferred to use a mixture of two or more triplet emitters and a host. A triplet emitter with a shorter wave emission spectrum is used here as a co-matrix for a triplet emitter with a longer wave emission spectrum.

In this case, the proportion of the host material in the light-emitting layer is preferably between 50 and 99.9% by volume, more preferably between 80 and 99.5% by volume for the fluorescent light-emitting layer, and most preferably Between 92 and 99.5% by volume, and between 85 and 97% by volume for the phosphorescent light-emitting layer.

Accordingly, the proportion of dopants is preferably between 0.1 and 50% by volume, more preferably between 0.5 and 20% by volume, and most preferably between 0.5 and 8% by volume for the fluorescent light-emitting layer % by volume, and for phosphorescent light-emitting layers between 3 and 15% by volume.

The emissive layer of an organic electroluminescent device may also comprise a system containing multiple host materials (mixed-matrix systems) and/or multiple dopants. Also in this case, the dopant is generally the smaller proportion of the material in the system, and the matrix material is the larger proportion of the material in the system. However, in individual cases, the proportion of individual host materials in the system may be smaller than the proportion of individual dopants.

The mixed matrix system preferably comprises two or three different matrix materials, more preferably two different matrix materials. Here one of the two materials is preferably a material with hole transport properties and the other material is a material with electron transport properties. However, the desired electron transport and hole transport properties of mixed matrix components can also be incorporated predominantly or completely in a single mixed matrix component, with other mixed matrix components fulfilling other functions. Here the two different matrix materials may be in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1 and optimally 1:4 to 1:1 exist. Mixed matrix systems are preferred for phosphorescent organic electroluminescent devices. Further details on mixed matrix systems can be found, for example, in WO 2010/108579.

In addition to these layers, the organic electroluminescent device may also comprise other layers, such as in each case one or more hole injection layers, hole transport layers, hole blocking layers, electron transport layers, electron injection layers, Exciton blocking layer, electron blocking layer, charge generating layer (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J . Kido, Multiphoton Organic EL Device Having Charge Generation Layer ) and/or organic or inorganic p/n junction. Here it is possible to p-dope one or more hole transport layers, for example with metal oxides, such as MoO ₃ or WO ₃ , or with (per)fluorinated electron-deficient aromatic compounds, and/or with a or more electron transport layers are n-doped. It is likewise possible to introduce an intermediate layer between the two light-emitting layers, which intermediate layer has, for example, an exciton blocking function and/or controls the charge balance in the electroluminescent device. However, it should be noted that each of these layers does not necessarily have to be present. These layers may likewise be present when using the formulations according to the invention, as defined above.

In another embodiment of the present invention, the device includes multiple layers. The formulations according to the present invention can preferably be used to manufacture hole transport layers, hole injection layers, electron transport layers, electron injection layers and/or emissive layers.

Accordingly, the present invention also relates to an electronic device comprising at least three of the hole injection, hole transport, emission, electron transport, electron injection, charge blocking and/or charge generating layers, but in preferred embodiments the All of the aforementioned layers are included, and at least one of which has been prepared from the formulation used according to the present invention. The thickness of layers such as hole transport and/or hole injection layers may preferably be in the range of 1 to 500 nm, more preferably in the range of 2 to 200 nm.

Furthermore the device may comprise a layer composed of other low molecular weight compounds or polymers not applied by using the formulations according to the invention. These can also be made by evaporating low molecular weight compounds in high vacuum.

It is also preferred to use the compound not as a pure substance, but as a mixture with any other desired type of polymeric, oligomeric, dendritic or low molecular weight substances. For example, these can improve their own electronic properties or emission.

In preferred embodiments of the present invention, the formulations according to the present invention comprise organic functional materials used as host materials or host materials for the light-emitting layer. The formulations here may also contain, in addition to the host material or matrix material, the emitters described above. The organic electroluminescent device herein may include one or more light-emitting layers. If there are multiple emissive layers, these preferably have multiple emission maxima between 380 nm and 750 nm, generally resulting in a white emission, ie the emissive layers use fluorescent or phosphorescent light-emitting Various emissive compounds. Very particular preference is given to a three-layer system, wherein the three layers exhibit blue, green and orange or red emission (for basic structure see eg WO 2005/011013). The white light-emitting device is suitable, for example, as a backlight for LCD displays or for general lighting applications.

It is also possible to arrange a plurality of OLEDs one after the other, making it possible to achieve a further increase in efficiency with respect to light output.

In order to improve the coupling-out of light, the final organic layer on the light-exit side of the OLED can also be in the form of nanofoam, for example, resulting in a reduction in the ratio of total reflection.

^Still more preferably an organic electroluminescent device in which one or more layers are applied by a ^sublimation process, wherein the The material was applied by vapour deposition in a vacuum sublimation unit at a pressure of 10 ⁻⁷ mbar.

Furthermore, it can be provided that one or more layers of the electronic device according to the invention are applied by an OVPD (Organic Vapour Deposition) process or by means of sublimation of a carrier gas, wherein the material is at a pressure between 10 ⁻⁵ mbar and 1 bar Apply down.

Furthermore, it may be provided that one or more layers of the electronic device according to the invention are manufactured from solution, for example by spin coating, or by any desired printing process, such as screen printing, flexographic printing or offset printing, but particularly preferred LITI (light induced thermal imaging, thermal transfer printing) or inkjet printing.

The device typically includes a cathode and an anode (electrode). The electrodes (cathode, anode) are chosen for the purposes of the present invention so that their band energies are as close as possible to the band energies of adjacent organic layers to ensure efficient electron or hole injection.

The cathode preferably comprises a metal complex, a metal with a low work function, a metal alloy, or comprises various metals such as alkaline earth metals, alkali metals, main group metals or lanthanides such as Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.) multilayer structure. In the case of multi-layer structures, in addition to the aforementioned metals, other metals with relatively high work functions such as Ag and Ag nanowires (Ag NWs) can also be used, in which case a combination of metals is generally used, for example, Ca/Ag or Ba/Ag. A thin intermediate layer of a material with a high dielectric constant may also preferably be introduced between the metal cathode and the organic semiconductor. Suitable for this purpose are, for example, alkali metal or alkaline earth metal fluorides, and corresponding oxides (eg LiF, _Li2O , BaF2, MgO, _NaF , etc.). The layer thickness of this layer is preferably between 0.1 and 10 nm, more preferably between 0.2 and 8 nm, and most preferably between 0.5 and 5 nm.

The anode preferably comprises a material with a high work function. The anode preferably has a potential greater than 4.5 eV relative to vacuum. Suitable for this purpose on the one hand are metals with a high redox potential, such as Ag, Pt or Au. On the other hand, metal/metal oxide electrodes (eg Al/Ni/ _NiOx , Al/ _PtOx ) may also be preferred. For some applications, at least one electrode must be transparent to facilitate illumination of organic materials (O-SCs) or outcoupling of light (OLEDs/PLEDs, O-lasers). A preferred structure uses a transparent anode. The preferred anode material here is a conductive mixed metal oxide. Particularly preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). Furthermore, conductive doped organic materials are preferred, especially conductive doped polymers such as poly(ethylenedioxythiophene) (PEDOT) and polyaniline (PANI) or derivatives of these polymers. Furthermore, it is preferred to apply a p-doped hole transport material as a hole injection layer to the anode, wherein suitable p-dopants are metal oxides, such as MoO ₃ or WO ₃ , or (per)fluorine Electron deficient aromatic compounds. Other suitable p-dopants are HAT-CN (hexacyanohexaazatriphenyl) or the compound NDP9 from Novaled. This type of layer simplifies hole injection in materials with low HOMO, ie with a large value of HOMO.

In general, all materials used for layers according to the prior art can be used for other layers, and those skilled in the art can combine each of these materials with materials according to the present invention in electronic devices without advancement.

The device is accordingly constructed in a manner known per se, depending on the application, providing a joint and ultimately a hermetic seal, since in the presence of water and/or air the lifetime of the device is significantly shortened.

The formulations according to the present invention and electronic devices obtained therefrom, especially organic electroluminescent devices, have one or more of the following surprising advantages over the prior art: 1. The electronic devices obtained using the formulations according to the present invention exhibit very high stability and very long lifetimes compared to electronic devices obtained using conventional methods. 2. The formulations according to the present invention can be processed by conventional methods so that cost advantages can be achieved. 3. The organic functional materials used in the formulation of the present invention are not subject to any specific limitations, and the process of the present invention can be widely applied. 4. The coatings obtained using the formulations of the present invention exhibit superior quality, especially the uniformity of the coating.

These above-mentioned advantages are not accompanied by the impairment of other electronic properties.

It should be noted that variations of the specific examples described herein are all within the scope of the present invention. Each feature disclosed herein may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Accordingly, each feature disclosed herein, unless otherwise specified, should be considered an example of a generic series or an equivalent or similar feature.

All features of the invention may be combined with each other in any way, unless certain features and/or steps are mutually exclusive. This applies in particular to the preferred features of the present invention. Likewise, features that are not necessarily combined may be used separately (rather than in combination).

Furthermore, it should be pointed out that many of the features, particularly those of the preferred embodiments of the invention, are progressive in their own right and should not be considered merely part of the embodiments of the invention. Independent protection may also be sought for these features in addition to or as an alternative to the presently claimed inventions.

The teachings of the technical documents disclosed herein can be abstracted and combined with other examples.

The invention is explained in more detail below with reference to working examples, but is not limited thereto.

Those skilled in the art can use this description to manufacture other electronic devices in accordance with the present invention without the use of inventive skills, and thus be able to practice the invention within the scope of the claims. working example A) Viscosity and sprayability

B) 膜形成 HTL inks were prepared and tested for viscosity and suitability for ink jet printing. The composition of the solvent mixture used to prepare the ink consisted of 1-phenylnaphthalene (PNA), cyclohexyl hexanoate (CHH), and Pentylbenzol (PYB), and is shown in Table 1. As the material of the hole transport layer, HTM with a concentration of 7 g/l was used. Jet performance was tested with a Dimatix DMP-2831 printer equipped with a 10 pl Dimatix cartridge. While maintaining the pulse width and pulse shape constants, the ligament lengths and voltages were recorded at different droplet velocities. The maximum droplet frequency with stable droplet ejection was also recorded. The information is collected in Table 2. It is clearly seen that these inks have superior ink jet printing properties.

B) Film formation

Six emissive layer (EML) inks were prepared as shown in Table 3. The materials used in green EML are H1, H2 and D1 in the relative ratio of 40/40/20, and the materials used in red EML are H1, H2, D1 and D2 in the ratio of 32/40/20/8. The total concentration is 12 to 20 g/l. The ink was ink jet printed and the film profile was measured after drying. The solvent 3-phenoxytoluene was chosen as a reference and showed a U-shaped film profile (Fig. 2). The film profile shows a significant improvement and a flat film can be achieved by adding two other solvents to 3-phenoxytoluene. In Example 2 and Example 3, different proportions of 1-phenylnaphthalene and pentylbenzene were added to achieve a flat film. In Example 4, a flat red EML was also achieved by applying a red EML containing the same solvent mixture as in Example 3. This solvent system was demonstrated to be useful for a variety of solid materials.

Furthermore, changing pentylbenzene to heptylbenzene also achieved a flat green EML, as shown in Example 5. In Example 6, the green EML was tested for a solvent combination containing 1-ethylnaphthalene, 1-phenylnaphthalene, and diethylene glycol butyl methyl ether. As a result, a flat film is achieved. The solvent combination ratio and the film flatness results of the above examples are summarized in Table 3. Film flatness measurement results and definitions are described below.

其中 橫越像素之短軸測量，

為像素邊緣之高度，且

為像素中心之高度。 Membrane profiles were measured using a profiler Alpha-step D120 from KLA-Tencor with a 2 [mu]m probe. The flatness factor is calculated and used to find the flatness by:

where measured across the short axis of the pixel,

is the height of the pixel edge, and

is the height of the pixel center.

C) 溶液安定性 A film is considered flat when the flatness factor is equal to or less than 10%.

C) Solution stability

D) 裝置性能 製程說明： To evaluate the suitability of solvent mixtures for their ink applications, inks were prepared and monitored under a series of conditions. The material was weighed according to the specified weight percentages to allow 5 ml of ink to be prepared. The solvent was purged with inert gas for 20 minutes and added to the solid. The solution was stirred until dissolved and then filtered. The clear solution was stored in a glass vial under argon in a freezer at -20°C for two weeks and the samples were checked for visible precipitation after warming to room temperature. In parallel experiments, the samples were stored in a refrigerator (6°C) and in the third case the inks were stored at room temperature. Precipitation was not observed in any case. This confirms that the solvent mixture according to the invention is very suitable for the preparation of long-term stable OLED inks.

D) Device performance process description:

The glass substrate covered with prestructured ITO and bank material was dried in isopropanol using ultrasonic waves, followed by deionized water cleaning, then using an air gun followed by annealing on a hot plate at 230°C for 2 hours.

The OLED has in principle the following layer structure: - substrate, - ITO (50 nm), - hole injection layer (20 nm), - hole transport layer (20 nm), - Emission Layer (EML) (60 nm), - Hole Blocking Layer (HBL) (10 nm) - Electron Transport Layer (ETL 50%, EIL 50%) (40 nm), - Electron Injection Layer (EIL) (1 nm), - Cathode. The cathode is formed from an aluminum layer with a thickness of 100 nm.

A hole injection layer (HIL) using hole transport, cross-linked polymer and p-doped salt was inkjet printed onto the substrate and dried in vacuum. Corresponding materials have been described in WO 2016/107668, WO 2013/081052 and EP 2325190. The examples used 1-ethylnaphthalene: 1-phenylnaphthalene (99:1) to prepare HIL inks at 7 g/l. The HIL was then annealed at 200 °C for 30 min in air.

On top of the HIL, a hole transport layer (HTL) was inkjet printed, dried in vacuo and annealed at 225°C for 30 minutes in a nitrogen atmosphere. As material for the hole transport layer, the polymer HTM dissolved in 3-phenoxytoluene:1-phenylnaphthalene (97:3) at a concentration of 7 g/l was used. Two green EML inks were prepared at 20 g/l with solvent Comparative Example 1 and Example 2 (Table 5). The green EML was also inkjet printed, vacuum dried and annealed at 150°C for 10 minutes in a nitrogen atmosphere. The inkjet printing process of HIL, HTL and EML was carried out with a Dimatix Pixdro LD50 printer and a Q-class printing head with a drop size of 10 pL. All inkjet printing processes are performed under yellow light and ambient conditions.

The device was then transferred into a vacuum deposition chamber where a common hole blocking layer (HBL), electron transport layer (ETL) and cathode (Al) were deposited by thermal evaporation. The electron transport layer can be a single electron transport molecule, or as in this case composed of two materials, mixed in a volume ratio by co-evaporation. The expression ETM1:ETM2 (50%:50%) here means that the material ETM1 is present in the layer in a proportion of 50% by volume and ETM2 is present in the layer in a proportion of 50%.

The chemical structures of materials including polymer HTM and green EML and ETL are shown in Table 6.

OLEDs are characterized by standard methods. For this purpose, a Lambertian emission profile is assumed, and the electroluminescence spectrum, current efficiency (measured in cd/A) and external quantum efficiency are determined from the current/voltage/luminance characteristic line (IVL characteristic line). (EQE, measured in % at 1000 ^cd /m2). Electroluminescence (EL) spectra were recorded at a luminous density of 1000 cd/m ² and CIE 1931 x and y coordinates were then calculated from the EL spectra. The EQE at 1000 cd/m² is defined as the external quantum efficiency at a luminous density of 1000 cd/m². For all experiments, the lifetime LT80 was determined. The LT80 lifetime at 8000 cd/m² was defined as the time after the initial luminous density of 8000 cd/m² dropped by 20%. Device data for various OLEDs are summarized in Table 7. It can be seen that Device Example 2 using the solvent combination achieves higher device performance and lifetime than Device Example 1 using the comparative solvent. It is indicated that the improvement in device performance is mainly attributable to the novelty of the solvent combination.

[Fig. 1] shows a substrate containing a substrate, an ITO anode, a hole injection layer (HIL), a hole transport layer (HTL), a green emission layer (G-EML), a hole blocking layer (HBL), an electron transport layer ( Typical layer structure of the device with ETL) and Al cathode.

[FIGS. 2 to 7] show film cross sections of the films prepared in Comparative Example 1 and Working Examples 2 to 6.

Claims (21)

A formulation containing at least one organic functional material and a mixture of three different organic solvents (first organic solvent A, second organic solvent B and third organic solvent C), characterized in that: - The boiling point of the first organic solvent A is in the range of 250 to 350°C and the viscosity is ≥10 mPas, - The boiling point of the second organic solvent B is in the range of 200 to 350°C and the viscosity is in the range of 2 to 5 mPas, - The boiling point of the third organic solvent C is in the range of 100 to 300°C and the viscosity is ≤3 mPas, - The solubility of the at least one organic functional material in the second organic solvent B is ≥5 g/l, and - The boiling point of the first organic solvent A is at least 10°C higher than the boiling point of the second organic solvent B. The formulation of claim 1, wherein the first organic solvent A is selected from the group consisting of naphthalene derivatives, partially hydrogenated naphthalene derivatives, fully hydrogenated naphthalene derivatives, indane derivatives and fully hydrogenated anthracene derivatives . The formulation of claim 1 or 2, wherein based on the total amount of solvent in the formulation, the content of the first organic solvent A is in the range of 0.1 to 50% by volume. The formulation of one or more of claims 1 to 3, wherein the boiling point of the first organic solvent A is in the range of 260 to 340°C. The formulation of one or more of claims 1 to 4, wherein the viscosity of the first organic solvent A is ≥15 mPas, preferably ≥25 mPas, and more preferably ≥50 mPas. The formulation of one or more of claims 1 to 5, wherein based on the total amount of solvent in the formulation, the content of the second organic solvent B is in the range of 20 to 85% by volume. The formulation of one or more of claims 1 to 6, wherein the boiling point of the second organic solvent B is in the range of 225 to 325°C. The formulation of one or more of claims 1 to 7, wherein the content of the third organic solvent C is in the range of 10 to 70% by volume based on the total amount of solvent in the formulation. The formulation of one or more of claims 1 to 8, wherein the boiling point of the third organic solvent C is in the range of 125 to 275°C. The formulation of one or more of claims 1 to 9, wherein the surface tension of the formulation is in the range of 10 to 70 mN/m. The formulation of one or more of claims 1 to 10, wherein the viscosity of the formulation is in the range of 0.8 to 50 mPas. The formulation of one or more of claims 1 to 11, wherein the at least one organic functional material is a low molecular weight compound with a molecular weight of ≤3,000 g/mol. The formulation of one or more of claims 1 to 11, wherein the at least one organic functional material is a polymeric compound with a molecular weight Mw≥10,000 g/mol. The formulation of one or more of claims 1 to 13, wherein the content of at least one organic functional material in the formulation is in the range of 0.001 to 20 wt % based on the total weight of the formulation. The formulation of one or more of claims 1 to 14, wherein the at least one organic functional material is selected from the group consisting of: organic conductors, organic semiconductors, organic fluorescent compounds, organic phosphorescent compounds, organic light absorbing compounds (organic light-absorbent compounds), organic light-sensitive compounds, organic photosensitizers and other organic photosensitive compounds such as organometallic complexes of transition metals, rare earth elements, lanthanides and actinides. The formulation of claim 15, wherein the at least one organic functional material is an organic semiconductor selected from the group consisting of: fluorescent emitters, phosphorescent emitters, host materials, host materials, exciton blocking materials -blocking material), electron transport material, electron injection material, hole transport material, hole injection material, n-type dopant, p-type dopant, wide-band-gap material, electron blocking material and hole blocking materials. The formulation of claim 16, wherein the at least one organic semiconductor is an emitter material selected from the group consisting of fluorescent emitters and phosphorescent emitters. The formulation of claim 17, wherein the at least one luminescent material is a mixture of two or more different compounds of low molecular weight. A method of preparing a formulation as claimed in one or more of claims 1 to 18, characterized in that the at least one organic functional material is mixed with the three different organic solvents A, B and C. A method of producing an electronic device, characterized in that a formulation as claimed in one or more of claims 1 to 18 is deposited, preferably printed, more preferably ink-jet printed on a surface, and then dried to produce at least one of the electronic devices. layer. An electronic device characterized in that at least one layer is prepared by depositing, preferably printing, more preferably inkjet printing, a formulation as claimed in one or more of claims 1 to 18 on a surface and then drying.

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